bluuebunny/crossref_metadata_2025_split huggingface dataset:
Continuous enzymatic interesterification of milkfat with soybean oil produces a highly spreadable product rich in polyunsaturated fatty acids
Authors: Paula Ariela V. , Nunes Gisele F. M. , Osório Natália M. , Santos Júlio C. , de Castro Heizir F. , Ferreira‐Dias Suzana 
Published: December 2014

AbstractThe aim of this study was to tune the physical properties of milkfat by enzymatic interesterification with soybean oil in a continuous fluidized bed reactor (FBR) to obtain healthy interesterified fat blends having suitable texture properties for the food industry. The immobilized commercial non‐regioselectiveCandida antarcticalipase (Novozym®435) andsn1,3‐regioselectiveRhizopus oryzaelipase, immobilized in an organic‐inorganic hybrid matrix of polysiloxane‐polyvinyl alcohol, were used as biocatalysts in a FBR. The minimum value of the ascendant flow of the medium for allowing fluidization in the system was 3.13 mL·min−1. The reaction was evaluated in terms of the interesterification yield (IY), consistency values and solid fat content (SFC). The IY values of 10.50 ± 1.64% and of 5.70 ± 1.46% were attained for Novozym®435 and for immobilizedR. oryzaelipase, respectively. The consistency of the initial 65:35 milkfat/soybean oil mixture (1000 gf/cm2) decreased to 732.35 ± 75.30 gf/cm2and to 478.02 ± 71.80 gf/cm2in interesterified blends catalyzed by Novozym®435 or byR. oryzaelipase, respectively. SFC was considered an inadequate parameter for following the interesterification of this blend formulation because the values were similar for initial and for interesterified blends. Free fatty acid levels of 1.5%, the non‐notable deactivation of Novozym®435 and a half‐life of 190 h forR. oryzaelipase were observed during the operation time.Practical applications:By interesterification of milkfat with soybean oil, a new product presenting higher spreadability than butter and richer in polyunsaturated fatty acids coming from soybean oil, was obtained. TheRhizopus oryzaelipase immobilized in an organic‐inorganic hybrid matrix, used in a FBR for the modification of milkfat, promoted a higher reduction (approximately 52.0%) in the consistency of the interesterified products in relation to the initial reaction mixture than that obtained with Novozym® 435 (approximately 27.0% reduction). Also, while Novozym® 435 is as a non‐specific lipase, theR. oryzaelipase presentssn‐1,3 regioselectivity, which enables the maintenance of the unsaturated fatty acids at positionsn‐2 in triacylglycerols with well‐known nutritional benefits. This biocatalyst showed a better performance than the immobilized commercial lipase (Novozym® 435). The implementation of the interesterification in a continuous FBR results in lower shear rate imposed on the biocatalyst.The consistency of the initial milkfat/soybean blend (65:35,% w/w) decreased about 52% or 27% after interesterification in a continuous fluidized bed reactor, catalyzed by the immobilized Rhizopus oryzae lipase or by Novozym 435, respectively.
Synthesis and Properties of 5,7‐Dihydropyrido[3,2‐b:5,6‐b′]diindoles
Authors: Hung Tran Quang , Thang Ngo Ngoc , Hoang Do Huy , Dang Tuan Thanh , Ayub Khurshid , Villinger Alexander , Lochbrunner Stefan , Flechsig Gerd‐Uwe , Langer Peter 
Published: December 2014

Abstract5,7‐Dihydropyrido[3,2‐b:5,6‐b′]diindoles were prepared by a highly efficient two‐step synthesis that involved a site‐selective Suzuki coupling reaction of 2,3,5,6‐tetrabromopyridine and a subsequent Pd‐catalyzed cyclization that proceeded through a twofold C–N coupling reaction with aromatic and aliphatic amines. With the exception of the parent molecule, which was described in a patent without any characterization data, the 5,7‐dihydropyrido[3,2‐b:5,6‐b′]diindoles are a new chemical entity. Their electrochemical and photochemical properties were investigated. These pyridodiindoles show promising fluorescence properties with good quantum yields and interesting electrochemical behavior. The optical and electronical properties were analyzed and explained by using DFT calculations.
AlCl3‐Catalyzed [3+2] Annulations of cis‐2,3‐Disubstituted Cyclopropane 1,1‐Diesters with Cyclic Ketones: Diastereoselective Construction of Spirotetrahydrofurans
Authors: Yang Gaosheng , Wang Tingting , Chai Jun , Chai Zhuo 
Published: December 2014

AbstractThe stereoselective [3+2] annulations of cis‐2,3‐disubstituted cyclopropane 1,1‐diesters with cyclic/acyclic aliphatic ketones were effected by AlCl3 to provide highly functionalized spirotetrahydrofurans in moderate to excellent yields under very mild conditions.
The Reversible Nicholas Reaction in the Synthesis of Highly Symmetric Natural‐Product‐Based Macrocycles
Authors: de la Torre María C. , Asenjo María , Ramírez‐López Pedro , Sierra Miguel A. 
Published: December 2014

AbstractTwo different approaches to highly symmetric macrocycles by reversible Nicholas reactions have been developed. The first sequence uses a bis[Co2(CO)6] complex derived from a double propargylic alcohol supporting two natural product moieties. The reactions with BF3·OEt2 and different benzene dimethanols yielded either (1:1) or (2:2) adducts, depending essentially on the nature of the tether joining both Co clusters. Alternatively, the Nicholas reactions of Co‐complexed propargyl alcohol templates with one steroid and one monoterpene fragment as well as one aromatic terminus containing an alcohol moiety yielded the corresponding macrocycles derived from self‐dimerization. Both routes to macrocycles are complementary and efficiently produce sophisticated natural‐product‐containing structures.
Lithium Choreography Determines Contrasting Stereochemical Outcomes of Aryl Migrations in Benzylic Carbamates, Ureas and Thiocarbamates
Authors: Vincent Mark A. , Maury Julien , Hillier Ian H. , Clayden Jonathan 
Published: December 2014

AbstractThe intramolecular arylation reactions of lithiated derivatives of ureas, carbamates and thiocarbamates generally proceed stereospecifically, but the reaction is stereochemically retentive with ureas and thiocarbamates, whereas it is stereochemically invertive with carbamates. Using DFT calculations, we have studied the mechanism of the intramolecular attack of a thiocarbamate‐stabilised carbanion on an N‐aryl substituent and compared the details of the calculated reaction pathway with the corresponding reactions of carbamate‐ and urea‐stabilised carbanions. The different stereochemical outcomes observed in the rearrangements of carbamates and thiocarbamates arise from the sulfur–carbon interaction in the thiocarbamate, which enhances the stabilisation of the anion. As a result, the solvated lithium cation takes different pathways across the potential energy surfaces that lead to stereochemically divergent outcomes. Additionally, we investigated the importance of the intramolecular nature of the aryl migration and compared the pathway for aryl migration within a urea with that of a hypothetical, experimentally unfeasible, intermolecular reaction. The results throw light on the reason why aryl migrations are successful even with much more electron‐rich rings than would be tolerated in a typical intermolecular nucleophilic aromatic substitution.
Overview review: Comparative efficacy of oral ibuprofen and paracetamol (acetaminophen) across acute and chronic pain conditions
Authors: Moore R.A. , Derry S. , Wiffen P.J. , Straube S. , Aldington D.J. 
Published: December 2014

AbstractBackgroundIbuprofen and paracetamol have long been used as analgesics in a range of acute, intermittent and chronic pain conditions. Paracetamol is often the first line analgesic recommended, without consensus about which is the better analgesic.MethodsAn overview review of systematic reviews and meta‐analyses directly compares ibuprofen and paracetamol at standard doses in particular painful conditions, or uses indirect comparisons against placebo. Electronic searches for systematic reviews were sought published since 1995 using outcomes approximating to ≥50% pain intensity reduction. Painful conditions were acute post‐operative pain, dysmenorrhoea, tension‐type headache (TTH), migraine, osteoarthritis and rheumatoid arthritis, back pain, cancer and paediatric pain. There was no systematic assessment of harm.ResultsSixteen systematic reviews and four individual patient data meta‐analyses were included. Ibuprofen was consistently superior to paracetamol at conventional doses in a range of painful conditions. Two direct comparisons favoured ibuprofen (acute pain, osteoarthritis). Three of four indirect comparisons favoured ibuprofen (acute pain, migraine, osteoarthritis); one showed no difference (TTH), although there were methodological problems. In five pain conditions (dysmenorrhoea, paediatric pain, cancer pain, back pain and rheumatoid arthritis), there were limited data on paracetamol and ibuprofen.ConclusionsAt standard doses in different painful conditions, ibuprofen was usually superior producing more patients with the degree of pain relief that patients feel worthwhile. Neither of the drugs will be effective for everyone, and both are needed. This overview questions the practice of routinely using paracetamol as a first line analgesic because there is no good evidence for efficacy of paracetamol in many pain conditions.
A Final Note About Improving Needs Assessment Research and Practice
Authors: Watkins Ryan , Altschuld James W. 
Published: December 2014

AbstractAs with any field of inquiry and application, needs assessment is an evolving topic of research and practice. The theories, models, tools, and approaches are not idle targets. In this chapter, the authors explore the emerging trends and issues of the field, suggesting elements of an exciting future and the continuing call for more research that can improve practice. They include an examination of how technologies are expanding the methods employed in assessments and a discussion of how many of the challenges that have nagged at assessors for decades continue to limit our results. The future for needs assessments remains bright, but much work remains to be done in order for needs assessment to mature as a field.
Extended vertical lower trapezius island myocutaneous flap versus pectoralis major myocutaneous flap for reconstruction in recurrent oral and oropharyngeal cancer
Authors: Chen Wei‐liang , Wang You‐yuan , Zhang Da‐ming , Fan Song , Lin Zhao‐yu 
Published: December 2014

AbstractBackgroundThe purpose of this study was to compare the use of an extended vertical lower trapezius island myocutaneous flap (TIMF) and a pectoralis major myocutaneous flap (PMMF).MethodsA total of 39 patients with advanced recurrent oral and oropharyngeal squamous cell carcinoma (SCC) underwent salvage surgery followed by placement of either an extended lower vertical TIMF or PMMF for reconstruction. Twenty‐one patients received extended lower vertical TIMFs, whereas 18 received PMMFs.ResultsThe pedicle length of the TIMF was longer than that of the PMMF, and the skin paddle of the TIMF was both wider and longer than the PMMF. No major complication developed in any of the patients. The TIMF group experienced a lower rate of minor flap failure than did the PMMF group.ConclusionUse of an extended vertical lower TIMF, which has a longer pedicle flap and a larger skin paddle than a PMMF, is optimal for reconstruction of major defects. © 2015 Wiley Periodicals, Inc. Head Neck 38: E159–E164, 2016
Critical Literacy and Social Justice
Authors: Comber Barbara 
Published: December 2014

AbstractGiven the global escalation of gaps between rich and poor, contemporary work in critical literacy needs to overtly question the politics of poverty. How and where is poverty produced, by what means, by whom and for whom and how are educational systems stratified to provide different kinds of education to the rich and the poor? Yet rather than critical literacy, international educational reform movements stress performative standards on basic literacy. In this context literacy researchers need to ask policy‐makers hard questions about taken‐for‐granted rhetoric that surrounds poverty, literacy and education. At school, regional and state levels, educational leaders need to argue for fair resourcing and decision‐making for their communities and students. In classrooms teachers need to weave critical questioning and inclusive learning interactions into the fabric of everyday life.
Enacting Critical Literacy in English Classrooms
Authors: Riley Kathleen 
Published: December 2014

AbstractIn a time of increased standardization and top‐down reform, teachers with democratic and social justice‐oriented perspectives must work to create classroom spaces that value student voice and position them as knowledge holders. This article draws on a critical literacy framework to analyze the case study of one teacher working within a teacher study group on adolescent literacy education in a large urban area. This teacher re‐articulated her values in the context of a constraining school culture, made sense of her practice in order to improve it, and considered how she might negotiate the micropolitical environment of her school. The article concludes with a discussion of how the study group provided structured support for this teacher's inquiry and discusses how teachers can work together to open more space for enacting critical literacy practices within constraining policy environments.
Role of the Parathyroid Hormone Type 1 Receptor (PTH1R) as a Mechanosensor in Osteocyte Survival
Authors: Maycas Marta , Ardura Juan A , de Castro Luis F , Bravo Beatriz , Gortázar Arancha R , Esbrit Pedro 
Published: December 2014

Abstract

Osteocytes have a major role in the control of bone remodeling. Mechanical stimulation decreases osteocyte apoptosis and promotes bone accrual, whereas skeletal unloading is deleterious in both respects. PTH1R ablation or overexpression in osteocytes in mice produces trabecular bone loss or increases bone mass, respectively. The latter effect was related to a decreased osteocyte apoptosis. Here, the putative role of PTH1R activation in osteocyte protection conferred by mechanical stimulation was assessed. Osteocytic MLO-Y4 cells were subjected to mechanical stimuli represented by hypotonic shock (216 mOsm/kg) or pulsatile fluid flow (8 Hz, 10 dynes/cm2) for a short pulse (10 min), with or without PTH1R antagonists or after transfection with specific PTHrP or PTH1R siRNA. These mechanical stimuli prevented cell death induced within 6 hours by etoposide (50 μM), related to PTHrP overexpression; and this effect was abolished by the calcium antagonist verapamil (1 μM), a phospholipase C (PLC) inhibitor (U73122; 10 μM), and a PKA activation inhibitor, Rp-cAMPS (25 μM), in these cells. Each mechanical stimulus also rapidly induced β-catenin stabilization and nuclear ERK translocation, which were inhibited by the PTH1R antagonist PTHrP(7–34) (1 μM), or PTH1R siRNA, and mimicked by PTHrP(1–36) (100 nM). Mechanical stretching by hypotonic shock did not affect cAMP production but rapidly (&lt;1 min) stimulated Cai2+ transients in PTH1R-overexpressing HEK-293 cells and in MLO-Y4 cells, in which calcium signaling was unaffected by the presence of a PTHrP antiserum or PTHrP siRNA but inhibited by knocking down PTH1R. These novel findings indicate that PTH1R is an important component of mechanical signal transduction in osteocytic MLO-Y4 cells, and that PTH1R activation by PTHrP-independent and dependent mechanisms has a relevant role in the prosurvival action of mechanical stimulus in these cells. © 2014 American Society for Bone and Mineral Research © 2014 American Society for Bone and Mineral Research
Structural study of a lead (II) organic complex – a key precursor in a green recovery route for spent lead‐acid battery paste
Authors: Zhang Wei , Yang Jiakuan , Zhu Xinfeng , Sun Xiaojuan , Yu Wenhao , Hu Yuchen , Yuan Xiqing , Dong Jinxin , Hu Jingping , Liang Sha , Kumar Ramachandran Vasant 
Published: December 2014

ABSTRACTBACKGROUNDLead citrate is an attractive precursor for the preparation of ultrafine leady oxide from the paste in spent lead‐acid batteries through a novel hydrometallurgical process, since the recovered lead oxide could be recycled for the production of new lead acid batteries.RESULTSTwo different metal organic complexes were synthesized from lead sulfate from the paste of spent lead‐acid batteries in a leaching solution at two different initial pH values. Single crystals of the two precursors were obtained by conditioning and filtering from the leached solutions, and used for single crystal XRD analysis. At an initial pH of 3.5, the chemical formula of Precursor‐I is deduced to be Pb(C6H6O7)·H2O while at an initial pH of 5.2, the chemical formula of Precursor‐II is Pb3(C6H5O7)2·3H2O.CONCLUSIONSBoth Precursor‐I and Precursor‐II crystallize in the triclinic crystal system, with space group P‐1. This structural study on precursors sheds light on the mechanism of a paste‐to‐paste recovery route for the recovery of spent lead paste. © 2014 Society of Chemical Industry
Hydrogen‐Bonding Effects for the C–ON Bond Homolysis and Reformation Reactions of Alkoxyamines
Authors: Bagryanskaya Elena G. , Brémond Paul , Butscher Teddy , Marque Sylvain R. A. , Parkhomenko Dmitry , Roubaud Valérie , Siri Didier , Viel Stéphane 
Published: December 2014

N‐(2‐methylpropyl)‐N‐(1‐diethylphosphono‐2,2‐dimethylpropyl)‐O‐(2‐carboxyprop‐2‐yl) hydroxylamine (BlocBuilder MA) is, among the commercially available alkoxyamines, one of the most efficient for nitroxide‐mediated polymerization (NMP). However, recent results have shown that it does not perform well for the NMP of isoprene. The occurrence of intramolecular hydrogen bonding (IHB) between the carboxylic function and the diethoxyphosphoryl group has been proposed as the reason for its low efficiency. In this article, the presence of this IHB is confirmed using IR, 31P NMR, 31P‐1H HOESY, and DFT calculation results. The solvent effect on this IHB and consequently on kd values is also investigated. However, combining kinetic analysis and rate measurements in various solvents, the influence of this IHB on the CON bond homolysis and reformation in alkoxyamine is shown to be very weak.
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Self‐Assembly of Amphiphilic Block Copolypeptoids with C2‐C5 Side Chains in Aqueous Solution
Authors: Fetsch Corinna , Flecks Silvana , Gieseler Dan , Marschelke Claudia , Ulbricht Juliane , van Pée Karl‐Heinz , Luxenhofer Robert 
Published: December 2014

Nowadays, amphiphilic molecules play an important role in our life. In medical applications, amphiphilic block copolymers have attracted much attention as excipients in drug delivery systems. Here, the polymers are used as emulsifiers, micelles, or polymersomes with a hydrophilic corona block and a hydrophobic core or membrane. The aggregation behavior in aqueous solutions of a series of different amphiphilic block copolypeptoids comprising polysarcosine as a hydrophilic part is here reported. The formation of aggregates is investigated with 1H NMR spectroscopy and dynamic light scattering, and the determination of the critical micelle concentration (cmc) is performed using pyrene fluorescence spectroscopy. For the different block copolypeptoids cmc values ranging from 0.6 × 10−6m to 0.1 × 10−3m are found. The tendency to form micelles increases with increasing hydrophobicity at the nitrogen side chain in the hydrophobic moiety. Furthermore, in the case of the same hydrophobic side chain, a decreasing hydrophilic/lipophilic balance leads to the formation of larger aggregates. The aggregates formed in the buffer are able to solubilize the hydrophobic model compounds Reichardt's dye and pyrene, and exhibit versatile microenvironments. Final investigations about the cytotoxicity reveal that the block copolypeptoids are well tolerated by mammalian cells up to high concentrations.
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The Self‐Healing Potential of Triazole‐Pyridine‐Based Metallopolymers
Authors: Sandmann Benedict , Happ Bobby , Kupfer Stephan , Schacher Felix H. , Hager Martin D. , Schubert Ulrich S. 
Published: December 2014

The development of artificial self‐healing materials represents an emerging and challenging field in material science. Inspired by nature—for instance by the self‐healing of mussel byssus threads—metallopolymers gain more and more attention as attractive self‐healing materials. These compounds are able to combine the properties of both polymers and metal–ligand interactions. A novel metallopolymer is developed consisting of attached bidentate triazole‐pyridine (TRZ‐py) ligands and a low glass transition temperature (T
g) lauryl methacrylate backbone. The polymer is cross‐linked with different Fe(II) and Co(II) salts. The resulting materials exhibit promising self‐healing performance within time intervals of 5.5 to 26.5 h at moderate temperatures of 50 to 100 °C. The materials are characterized by X‐ray scattering (SAXS), UV–Vis spectroscopy, and light microscopy.
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pH‐Switchable Self‐Assembled Materials
Authors: Frisch Hendrik , Besenius Pol 
Published: December 2014

Self‐assembled materials, which are able to respond to external stimuli, have been extensively studied over the last decades. A particularly exciting stimulus for a wide range of biomedical applications is the pH value of aqueous solutions, since deprotonation‐protonation events are crucial for structural and functional properties of biopolymers. In living cells and tissues, intra‐ and extracellular pH values are stringently regulated, but can deviate from pH neutral as observed for example in tumorous, inflammatory sites, in endocytic pathways, and specific cellular compartments. By using a pH‐switch as a stimulus, it is thereby possible to address specific targets in order to cause a programmed response of the supramolecular material. This strategy has not only been successfully applied in fundamental research but also in clinical studies. In this feature article, current strategies that have been used in order to design materials with pH‐responsive properties are illustrated. This discussion only addresses selected examples from the last four years, the self‐assembly of polymer‐based building blocks, assemblies emerging from small molecules including surfactants or derived from biological macromolecules, and finally the controlled self‐assembly of oligopeptides.
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Targeted Prodrug Approaches for Hormone Refractory Prostate Cancer
Authors: Aloysius Herve , Hu Longqin 
Published: December 2014

AbstractDue to the propensity of relapse and resistance with prolonged androgen deprivation therapy (ADT), there is a growing interest in developing non‐hormonal therapeutic approaches as alternative treatment modalities for hormone refractory prostate cancer (HRPC). Although the standard treatment for HRPC consists of a combination of ADT with taxanes and anthracyclines, the clinical use of chemotherapeutics is limited by systemic toxicity stemming from nondiscriminatory drug exposure to normal tissues. In order to improve the tumor selectivity of chemotherapeutics, various targeted prodrug approaches have been explored. Antibody‐directed enzyme prodrug therapy (ADEPT) and gene‐directed enzyme prodrug therapy (GDEPT) strategies leverage tumor‐specific antigens and transcription factors for the specific delivery of cytotoxic anticancer agents using various prodrug‐activating enzymes. In prostate cancer, overexpression of tumor‐specific proteases such as prostate‐specific antigen (PSA) and prostate‐specific membrane antigen (PSMA) is being exploited for selective activation of anticancer prodrugs designed to be activated through proteolysis by these prostate cancer‐specific enzymes. PSMA‐ and PSA‐activated prodrugs typically comprise an engineered high‐specificity protease peptide substrate coupled to a potent cytotoxic agent via a linker for rapid release of cytotoxic species in the vicinity of prostate cancer cells following proteolytic cleavage. Over the past two decades, various such prodrugs have been developed and they were effective at inhibiting prostate tumor growth in rodent models; several of these prodrug approaches have been advanced to clinical trials and may be developed into effective therapies for HRPC.