bluuebunny/crossref_metadata_2025_split huggingface dataset:
Low‐dose amphotericin b lipid complex vs. conventional amphotericin B for empirical antifungal therapy of neutropenic fever in patients with hematologic malignancies – a randomized, controlled trial
Authors: Subirà Maricel , Martino Rodrigo , Gómez Lucia , Martí Josep María , Estany Cristina , Sierra Jorge 
Published: April 2004

Abstract:Background:  Conventional amphotericin B (c‐AmB) remains the empirical antifungal treatment of choice for neutropenic patients with persistent fever of unknown origin (FUO). Unfortunately, empirical treatment with c‐AmB is hampered by its safety profile, with frequent infusion‐related adverse events (IRAEs) and renal toxicity. Amphotericin B lipid complex (ABLC) has been investigated for this indication due to its low toxicity profile. The recommended dose of ABLC is 5 mg/kg/d, which is five to seven times higher than the recommended dose of c‐AmB.Methods:  This randomized, controlled trial includes 105 adult patients with hematologic malignancies and with FUO after receiving chemotherapy or autologous stem cell transplantation. Patients were randomly allocated to receive ABLC at 1 mg/kg/d or c‐AmB at 0.6 mg/kg/d for empirical antifungal therapy.Results:  The incidence of renal toxicity was significantly lower in the ABLC group, compared with c‐AmB group: 8% vs. 32%, respectively (P = 0.003). The rates of IRAEs were similar in both groups (73% for ABLC vs. 77% for c‐AmB). The overall response rate was 72% for ABLC compared with 48% for c‐AmB (P = 0.018). This difference was mainly due to the significantly higher renal toxicity in the c‐AmB group. The number of emergent fungal infections and overall mortality were similar in both groups.Conclusions:  This randomized trial suggests that ABLC at 1 mg/kg/d produces less nephrotoxicity than c‐AmB, without differences in the incidence of IRAEs and with similar efficacy.
A real‐life event enhances the accuracy of preschoolers' recall
Authors: Thierry Karen L. , Spence Melanie J. 
Published: March 2004

AbstractChildren's memory and susceptibility to misinformation about a real‐life and video event were examined. Eighty‐six three‐ to four‐year‐olds and five‐ to six‐year‐olds observed an event either in real life or on video. Immediately afterward, they freely recalled the event and answered misleading questions about central and descriptive information. Three‐ to four‐year‐olds in the video condition were less likely to accurately recall descriptive information than three‐ to four‐year‐olds in the live condition and five‐ to six‐year‐olds in either condition. Children in the video condition were less accurate in response to misleading questions than those in the live condition. When video condition three‐ to four‐year‐olds in Experiment 2 were asked nonmisleading questions that prompted them for descriptive information, they recalled descriptors less accurately than those in the live condition. These results have particularly important implications for studies that utilize video events when investigating children's eyewitness memory. Copyright © 2004 John Wiley & Sons, Ltd.
Secrecy and suggestibility: are children's memories for secrets less suggestible than other memories?
Authors: Wilson J. Clare , Powell Martine B. , Raju Sadhana , Romeo Rosanna 
Published: March 2004

AbstractAdult secrecy research has found a memory‐enhancing effect for information kept secret as the secret is mentally rehearsed each time the adult is required to prevent it being reported (e.g. Lane & Wegner, 1994). The present study examined possible memory‐enhancing effects of children keeping information secret. Two hundred and thirty two five to eight year olds took part in a puppet‐making task. During the task the puppet‐maker sprayed glitter onto the puppets. Half the children were told to keep a secret (that the spray had been taken from Disneyland) and the other half (the control group) were merely told the spray was from Disneyland. One week later the children were interviewed either by the puppet‐maker (the secret‐giver) or by the puppet‐maker's friend (the secret‐novice). The five to six year olds showed no effect of the secret condition, whereas the seven to eight year olds made significantly less errors in their free recall in the secret condition compared to the control condition. There was no effect of the secret condition on children's suggestibility to leading questions. However, both age groups were significantly more suggestible when interviewed by the secret‐giver. Finally, both age groups showed a recall deficit in the secret condition. Copyright © 2004 John Wiley & Sons, Ltd.
Earwitnesses: effects of speech duration, retention interval and acoustic environment
Authors: Kerstholt José H. , Jansen Noortje J. M. , Van Amelsvoort Adri G. , Broeders A. P. A. 
Published: March 2004

AbstractAn experiment was conducted to investigate the reliability of voice lineups. More specifically, the experiment was designed to look into the effects of retention interval (an immediate test or after a week), speech duration (30 or 70 s) and acoustic environment (indoors or indoors and outdoors) on speaker identification accuracy. In addition, the relation between confidence assessments of both participants and test assistant on the one hand and identification accuracy was explored. A total of 361 participants heard the target voice in one of four exposure conditions (short or long text and speech samples recorded only indoors or indoors and outdoors). Half the participants were tested immediately after exposure to the target voice and half 1 week later. The results show that the target was correctly identified in 42% of cases. In the target‐absent condition there were 51% false alarms. Acoustic environment did not affect identification accuracy. There was an interaction between speech duration and retention interval in the target‐absent condition. When listeners were tested after a week, they made fewer false identifications if the speech sample was long. No effects were found when participants were tested immediately. Only the confidence scores of the test assistant had predictive value. Taking the confidence score of the test assistant into account therefore increases the diagnostic value of the identity parade. Copyright © 2004 John Wiley & Sons, Ltd.
α‐Hydroxylation of β‐Dicarbonyl Compounds
Authors: Christoffers Jens , Baro Angelika , Werner Thomas 
Published: March 2004

AbstractThe most convenient and direct route to α‐hydroxy‐β‐dicarbonyl compounds is the oxidation of readily accessible 1,3‐dicarbonyls. Hence, this type of oxidation is an intensively investigated field. In this short review, we present and compare α‐hydroxylations using various oxidants such as peracids (Rubottom oxidation), dimethyldioxirane or molecular oxygen. From an economical and ecological point of view, metal‐catalyzed air oxidations are optimal at least for cyclic β‐dicarbonyls. For asymmetric α‐hydroxylations only chiral sulfonyloxaziridines are available to date. Thus, there is still a need for significant development in this area.
Ruthenium‐Catalyzed Asymmetric Alkene Epoxidation with tert‐Butyl Hydroperoxide as Oxidant
Authors: Bhor Santosh , Tse Man Kin , Klawonn Markus , Döbler Christian , Mägerlein Wolfgang , Beller Matthias 
Published: March 2004

AbstractA ruthenium‐catalyzed asymmetric epoxidation of various olefins using tert‐butyl hydroperoxide (TBHP) as the oxidant is reported. By applying ruthenium(pyridinebisoxazoline)‐(pyridinedicarboxylate) complexes 1 [Ru(pybox)(pydic), 1] as catalysts, aromatic and aliphatic olefins yielded the corresponding epoxides at room temperature in good to excellent yields and enantioselectivities up to 65% ee. Slow addition of the stoichiometric oxidant significantly improved the yield and the chemoselectivity of the reaction.
Oxidations Catalyzed by Metallocorroles
Authors: Gross Zeev , Gray Harry B. 
Published: March 2004

AbstractMetallocorroles, in particular those containing chromium, manganese, and iron, have been found to be efficient catalysts for oxidation reactions. This review deals with work on hydrocarbon oxidations after the 1999 advance made in corrole synthesis that sparked the Technion‐Caltech collaborative program.
Hydrogen Peroxide Oxygenation of Alkanes Including Methane and Ethane Catalyzed by Iron Complexes in Acetonitrile
Authors: Shul'pin Georgiy B. , Nizova Galina V. , Kozlov Yuriy N. , Gonzalez Cuervo Laura , Süss‐Fink Georg 
Published: March 2004

AbstractThis paper describes an investigation of the alkane oxidation with hydrogen peroxide in acetonitrile catalyzed by iron(III) perchlorate (1), iron(III) chloride (2), iron(III) acetate (3) and a binuclear iron(III) complex with 1,4,7‐triazacyclononane (4). The corresponding alkyl hydroperoxides are the main products. Nevertheless in the kinetic study of cyclohexane oxidation, the concentrations of oxygenates (cyclohexanone and cyclohexanol) were measured after reduction of the reaction solution with triphenylphosphine (which converts the cyclohexyl hydroperoxide to the cyclohexanol). Methane and ethane can be also oxidized with TONs up to 30 and 70, respectively. Chloride anions added to the oxidation solution with 1 activate the perchlorate iron derivative in acetonitrile, whereas the water as additive inactivates 2 in the H2O2 decomposition process. Pyrazine‐2‐carboxylic acid (PCA) added to the reaction mixture decreases the oxidation rate if 1 or 2 are used as catalysts, whereas compounds 3 and 4 are active as catalysts only in the presence of small amount of PCA. The investigation of kinetics and selectivities of the oxidations demonstrated that the mechanisms of the reactions are different. Thus, in the oxidations catalyzed by the 1, 3+PCA and 4+PCA systems the main oxidizing species is hydroxyl radical, and the oxidation in the presence of 2 as a catalyst has been assumed to proceed (partially) with the formation of ferryl ion, (FeIVO)2+. In the oxidation catalyzed by the 4+PCA system (TONs attain 240) hydroxyl radicals were generated in the rate‐determining step of monomolecular decomposition of the iron diperoxo adduct containing one PCA molecule. A kinetic model of the process which satisfactorily describes the whole set of experimental data was suggested. The constants of supposed equilibriums and the rate constant for the decomposition of the iron diperoxo adduct with PCA were estimated.
A Simple and Highly Selective Biomimetic Oxidation of Alcohols and Epoxides with N‐Bromosuccinimide in the Presence of β‐Cyclodextrin in Water
Authors: Krishnaveni N. Srilakshmi , Surendra K. , Rama Rao K. 
Published: March 2004

AbstractA simple, mild and highly efficient biomimetic oxidation of various alcohols and epoxides with N‐bromosuccinimide (NBS) catalyzed by β‐cyclodextrin in water has been developed. A series of alcohols and epoxides were oxidized selectively at room temperature in excellent yields. This method is a direct one‐pot synthesis under mild conditions using water as solvent and has many advantages over the existing methodologies.
Fluorinated Silica Gels Doped with TPAP as Effective Aerobic Oxidation Catalysts in Dense Phase Carbon Dioxide
Authors: Ciriminna Rosaria , Campestrini Sandro , Pagliaro Mario 
Published: March 2004

AbstractHybrid organic‐inorganic fluorinated silica glasses doped with the ruthenium species TPAP (tetra‐n‐propylammonium perruthenate) are effective catalysts for the aerial oxidation of benzyl alcohol to benzaldehyde in dense phase CO2. Moderate silica fluorination (10%) by short‐chain fluoroalkyl‐containing monomers in the sol‐gel polycondensation with TMOS affords highly active catalysts which at 75 °C and 220 bar selectively dehydrogenate the alcohol with oxygen as primary oxidant. Both the activity and the stability of the fluorinated materials vary with the degree of fluorination and the nature of the fluoroalkyl residue attached to the silica polymeric network. An explanation of the behaviour of doped sol‐gel oxides in supercritical carbon dioxide is proposed which is thought to be of general validity for future practical applications to heterogeneously catalysed aerobic oxidations eliminating the current need for both organic solvents and stoichiometric oxidants.
Aerobic Oxidation of 1‐Phenylethanol Catalyzed by Palladaheterocycles
Authors: Paavola Sari , Zetterberg Krister , Privalov Timofei , Csöregh Ingeborg , Moberg Christina 
Published: March 2004

AbstractCyclometallated palladium compounds with pyridine were shown to serve as more efficient catalysts for the aerobic oxidation of 1‐phenylethanol than a previously investigated analogue with an oxazoline ring. Substituents with different electronic properties in the phenyl ring were shown to exhibit an only minor influence on the reactivity of the catalytic system. The first step in the reaction consists of the splitting of the acetate bridge in the dimeric starting complex and coordination of a ligand to palladium. By ab initio calculations it was shown that, in the presence of solvent, a complex with pyridine was more stable than that with the alcohol, whereas the opposite situation was found in the gas phase. The complex with coordinated alcohol was stabilized by hydrogen bonding. Good agreement was found between the computed structure and the X‐ray structure of the initial palladaheterocycle 1.
Synthesis of Naphthalenediols by Aerobic Oxidation of Diisopropylnaphthalenes Catalyzed by N‐Hydroxyphthalimide (NHPI)/α,α′‐Azobisisobutyronitrile (AIBN)
Authors: Aoki Yasuhiro , Sakaguchi Satoshi , Ishii Yasutaka 
Published: March 2004

AbstractNaphthalenediols were successfully synthesized in a one‐pot reaction through the oxidation of diisopropylnaphthalenes with air catalyzed by N‐hydroxyphthalimide (NHPI) combined with α,α′‐azobisisobutyronitrile (AIBN) followed by decomposition with sulfuric acid. Thus, the oxidation of 2,6‐diisopropylnaphthalene with air (20 atm) in the presence of AIBN (3 mol %) and NHPI (10 mol %) in CH3CN at 75 °C for 21 h followed by treatment with 0.3 M H2SO4 gave 2,6‐naphthalenediol in 92% yield.
Biocatalytic Oxidation of Primary and Secondary Alcohols
Authors: Kroutil Wolfgang , Mang Harald , Edegger Klaus , Faber Kurt 
Published: March 2004

AbstractDriven by the immaturity of many organic oxidation reactions and the necessity for ‘green’ chemical processes, biocatalytic redox processes are being investigated with increasing intensity in order to tap the full potential of the excellent chemo‐, regio‐ and enantioselectivity of enzymes. Despite their unmatched advantage in view of environmental aspects, the requirement of cofactors and the availability of redox enzymes able to tolerate high concentrations of organic (co)substrates sets limitations. However, during the past years, an increasing number of applications to the bio‐oxidation of primary and secondary alcohols with novel redox enzymes have been developed. This review gives an overview on the different methods and their potential and limits.
Photooxygenation in Polystyrene Beads with Covalently and Non‐Covalently Bound Tetraarylporphyrin Sensitizers
Authors: Griesbeck Axel G. , El‐Idreesy Tamer T. , Bartoschek Anna 
Published: March 2004

AbstractTwo reaction protocols are described which involve the use of polymer supports as reaction media for photooxygenation processes: 1) The use of polystyrene beads (PS) loaded with tetraphenyl‐ (TPP) or tetratolylporphyrin (TTP), swollen with the substrate in an appropriate organic solvent and subsequent irradiation under air. Products were isolated simply by dissolution in alcoholic solvents and filtration. 2) Covalently linked tetrastyrylporphyrin in polystyrene‐divinylbenzene beads were synthesized by emulsifier‐free emulsion polymerization and directly used for the photooxygenation protocol described above. The latter alternative allows also the use of less polar solvents for the extraction of the oxygenation products from the polymer beads. From the sensitizer loading degree, an optimal substrate/sensitizer molar ratio of 1,000–2,000 was determined and recyclization is possible for at least five times resulting in a minimum turnover number (with respect to the sensitizer TTP) of 5×104 (after five cycles). Both approaches were applied to the ene reaction of singlet oxygen with citronellol (1), the regioisomeric pinenes 3 and 5, and the allylic alcohols 9a–c, respectively, as well as to the [4+2]‐cycloadditions of singlet oxygen to sorbinol (7) and the chiral diene 11.
Microbial Transformations, 56. Preparative Scale Asymmetric Baeyer–Villiger Oxidation using a Highly Productive “Two‐in‐One” Resin‐Based in situ SFPR Concept
Authors: Hilker Iris , Alphand Véronique , Wohlgemuth Roland , Furstoss Roland 
Published: March 2004

AbstractAn efficient preparative scale process for achieving asymmetric Baeyer–Villiger oxidation – a reaction still very difficult to perform using conventional chemistry – is described. This process is based on a biocatalytic whole cells strategy – using a recombinant E. coli strain overexpressing cyclohexanone monooxygenase (CHMO) – combined with a “two‐in‐one” in situ “substrate feeding and product removal” concept (SFPR) using an adsorbent resin. The most efficient resin out of fourteen tested was used in three types of bioreactors (conventional, recycle and bubble column) that were compared. The best one proved to be the bubble column reactor, where 25 g (0.23 M) of rac‐bicyclo[3.2.0]hept‐2‐en‐6‐one could be totally transformed using a one‐litre vessel with a volumetric productivity of about 1 g L−1 h−1 (i.e., 7.7 mmol L−1 h−1). This led to the production of the two corresponding regioisomeric lactones, which were both obtained in excellent enantiomeric purity (ee>98%) and high preparative yield (84%). To our knowledge, these results represent the best example of a (highly productive) preparative scale asymmetric Baeyer–Villiger oxidation.
The Complex Synergy of Water in the Metal/Bromide Autoxidation of Hydrocarbons Caused by Benzylic Bromide Formation
Authors: Partenheimer Walt 
Published: March 2004

AbstractOne of the most active and selective catalysts in homogeneous liquid phase oxidation using molecular oxygen (O2) is a mixture of cobalt, manganese and bromide salts in acetic acid. It has been used to produce hundreds of different carboxylic acids in high yield and purity including the commercial production of terephthalic acid from p‐xylene. Water is normally a by‐product in these reactions and it is shown here that its concentration is an important reaction variable. In anhydrous acetic acid, with reagents with sufficiently strong electron‐withdrawing substitutents (toluene, 4‐carboxytoluene, 4‐chlorotoluene), all of the active bromide becomes inactive via benzylic bromide formation. The Co/Mn/Br catalyst is therefore converted to a Co/Mn catalyst which is dubbed ‘catalyst failure’ because of its undesirable characteristics of lower activity, decreased selectivity especially towards over‐oxidation and color formation. For 4‐chlorotoluene, increasing the water concentration to 5 weight % initially decreases the rate of reaction but eventually is more active and selective because the oxidation and hydrolysis of the benzylic bromide allows for sufficient active catalytic bromide. It is shown that benzylic bromides do not ‘promote’ the reaction and that both oxidation and solvolysis of the benzylic bromide occurs during autoxidation. During polymethylbenzene oxidation, benzylic bromide formation occurs only with the most reactive methyl group. The complex factors during metal/bromide autoxidation – some favored by increased water concentration and others detrimental – are outlined.
Catalytic Enantioselective Oxidation of Alkanes and Alkenes Using (Salen)Manganese Complexes Bearing a Chiral Binaphthyl Strapping Unit
Authors: Murahashi Shun‐Ichi , Noji Satoru , Komiya Naruyoshi 
Published: March 2004

AbstractA (salen)manganese(III) complex bearing a chiral binaphthyl strapping unit catalyzes the enantioselective hydroxylation of indane (up to 34% ee) and the epoxidation of alkenes (up to 93% ee) with iodosylbenzene.
Biomimetic Chemical Catalysts in the Oxidative Activation of Drugs
Authors: Bernadou Jean , Meunier Bernard 
Published: March 2004

AbstractAn overview of the biomimetic catalysts used in the oxidative activation of drugs is given, with an emphasis on the use of synthetic metalloporphyrins as models of cytochrome P450 to mimic the in vivo metabolism of pharmaceuticals. In addition, a special focus is directed towards the recent results from the authors' group on the oxidative activation of isoniazid, an antitubercular drug.
Aerobic Oxidation of Cycloalkanes, Alcohols and Ethylbenzene Catalyzed by the Novel Carbon Radical Chain Promoter NHS (N‐Hydroxysaccharin)
Authors: Baucherel Xavier , Gonsalvi Luca , Arends Isabel W. C. E. , Ellwood Simon , Sheldon Roger A. 
Published: March 2004

AbstractReplacement of Ishii's N‐hydroxyphthalimide (NHPI) with the novel carbon radical chain promoter N‐hydroxysaccharin (NHS) affords, in combination with metal salts, notably Co, or other additives, selective catalytic autoxidation of hydrocarbons, alcohols and alkylbenzenes under mild conditions (25–100 °C, O2 1 atm). The effects of solvent, temperature and the nature of the additives were investigated to give an optimised oxidation protocol for the various systems. The NHS/Co combination was more reactive than NHPI/Co in the autoxidation of cycloalkanes. In contrast, the opposite order of reactivity was observed in the autoxidation of ethylbenzene and alcohols. It is suggested, on the basis of bond dissociation energy (BDE) considerations, that this is a result of a change in the rate‐limiting step with the more reactive ethylbenzene and alcohol substrates. In the autoxidation of the model cycloalkane, cyclododecane, the best results (90% selectivity to a 4 : 1 mixture of alcohol and ketone at 24% conversion) were obtained with NHS/Co(acac)3 in PhCF3 at 80 °C. Competition experiments revealed that, in contrast to what is commonly believed, formation of the dicarboxylic acid by ring opening is not a result of further oxidation of the ketone product. It is suggested that ring opened products are a result of ß‐scission of the cycloalkoxy radical formed via (metal‐catalysed) decomposition of the hydroperoxide. This is suppressed in the presence of NHS (or NHPI) which efficiently scavenge the alkoxy radicals.
In situ Formation of Peracetic Acid in Iron‐Catalyzed Epoxidations by Hydrogen Peroxide in the Presence of Acetic Acid
Authors: Fujita Megumi , Que Lawrence 
Published: March 2004

AbstractIron complexes (tpa)Fe(OTf)2 (1) and (bpmen)Fe(OTf)2 (2) [tpa=tris‐(2‐pyridylmethyl)amine; bpmen=N,N′‐bis‐(2‐pyridylmethyl)‐N,N′‐dimethyl‐1,2‐ethylenediamine] were found to catalyze the in situ formation of AcOOH from H2O2 and AcOH in the course of olefin oxidations. While oxidation of cyclooctene by H2O2 catalyzed by 1 gives nearly equimolar epoxide and cis‐diol products, introduction of AcOH to the reaction greatly enhances the selectivity for epoxidation. The resulting product distribution is nearly identical to that of cyclooctene oxidation by AcOOH catalyzed by 1. The in situ generation of AcOOH from H2O2 and AcOH in epoxidation catalyzed by some iron complexes opens a possibility to attain AcOOH‐type efficiency of epoxidation using H2O2 as a terminal oxidant.