bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hypervalent Iodine‐Catalyzed Oxidative Functionalizations Including Stereoselective Reactions
Authors: Singh Fateh V. , Wirth Thomas 
Published: February 2014

AbstractHypervalent iodine chemistry is now a well‐established area of organic chemistry. Novel hypervalent iodine reagents have been introduced in many different transformations owing to their mild reaction conditions and environmentally friendly nature. Recently, these reagents have received particular attention because of their applications in catalysis. Numerous hypervalent iodine‐catalyzed oxidative functionalizations such as oxidations of various alcohols and phenols, α‐functionalizations of carbonyl compounds, cyclizations, and rearrangements have been developed successfully. In these catalytic reactions stoichiometric oxidants such as mCPBA or oxone play a crucial role to generate the iodine(III) or iodine(V) species in situ. In this Focus Review, recent developments of hypervalent iodine‐catalyzed reactions are described including some asymmetric variants. Catalytic reactions using recyclable hypervalent iodine catalysts are also covered.
Sex prevalence of major congenital anomalies in the United Kingdom: A national population‐based study and international comparison meta‐analysis
Authors: Sokal Rachel , Tata Laila J. , Fleming Kate M. 
Published: February 2014

BackgroundThe aim of this study was to assess sex differences in major congenital anomaly (CA) diagnoses within a national population sample; to examine the influence of sociodemographic and maternal factors on these risks; and to conduct a meta‐analysis using estimates from other population‐based studies.MethodsWe conducted a population‐based study in a United Kingdom research database of prospectively collected primary care data (The Health Improvement Network) including children born 1990 to 2009 (n = 794,169) and identified major CA diagnoses using EUROCAT (European Surveillance of Congenital Anomalies) classification. Prevalence ratios (PR) were used to estimate the risk of CA in males compared with females for any CA, system‐specific subgroups and specific CA diagnoses. In a subpopulation of children whose medical records were linked to their mothers', we assessed the effect of adjusting for sociodemographic and maternal factors on sex odds ratios. PRs were pooled with measures from previously published studies.ResultsThe prevalence of any CA was 307/10,000 in males (95% CI, 302–313) and 243/10,000 in females (95% CI, 238–248). Overall the risk of any CA was 26% greater in males (PR (male: female) 1.26, 95% CI, 1.23–1.30) however there was considerable variation across specific diagnoses. The magnitude and direction of risk did not change for any specific CA upon adjustment for sociodemographic and maternal factors. Our PRs were highly consistent with those from previous studies.ConclusionThe overall risk of CA is greater in males than females, although this masked substantial variation by specific diagnoses. Sociodemographic and maternal factors do not appear to affect these risks. Birth Defects Research (Part A) 100:79–91, 2014. © 2014 Wiley Periodicals, Inc.
Chlorite dismutases – a heme enzyme family for use in bioremediation and generation of molecular oxygen
Authors: Hofbauer Stefan , Schaffner Irene , Furtmüller Paul G. , Obinger Christian 
Published: February 2014

AbstractChlorite is a serious environmental concern, as rising concentrations of this harmful anthropogenic compound have been detected in groundwater, drinking water, and soil. Chlorite dismutases (Clds) are therefore important molecules in bioremediation as Clds catalyze the degradation of chlorite to chloride and molecular oxygen. Clds are heme b‐containing oxidoreductases present in numerous bacterial and archaeal phyla. This review presents the phylogeny of functional Clds and Cld‐like proteins, and demonstrates the close relationship of this novel enzyme family to the recently discovered dye‐decolorizing peroxidases. The available X‐ray structures, biophysical and enzymatic properties, as well as a proposed reaction mechanism, are presented and critically discussed. Open questions about structure‐function relationships are addressed, including the nature of the catalytically relevant redox and reaction intermediates and the mechanism of inactivation of Clds during turnover. Based on analysis of currently available data, chlorite dismutase from “Candidatus Nitrospira defluvii” is suggested as a model Cld for future application in biotechnology and bioremediation. Additionally, Clds can be used in various applications as local generators of molecular oxygen, a reactivity already exploited by microbes that must perform aerobic metabolic pathways in the absence of molecular oxygen. For biotechnologists in the field of chemical engineering and bioremediation, this review provides the biochemical and biophysical background of the Cld enzyme family as well as critically assesses Cld's technological potential.
The role of substrate binding pocket residues phenylalanine 176 and phenylalanine 196 on Pseudomonas sp. OX1 toluene o‐xylene monooxygenase activity and regiospecificity
Authors: Sönmez Burcu , Yanık‐Yıldırım K. Cansu , Wood Thomas K. , Vardar‐Schara Gönül 
Published: February 2014

ABSTRACTSaturation mutagenesis was used to generate eleven substitutions of toluene‐o‐xylene monooxygenase (ToMO) at alpha subunit (TouA) positions F176 and F196 among which nine were novel: F176H, F176N, F176S, F176T, F196A, F196L, F196T, F196Y, F196H, F196I, and F196V. By testing the substrates phenol, toluene, and naphthalene, these positions were found to influence ToMO oxidation activity and regiospecificity. Specifically, TouA variant F176H was identified that had 4.7‐, 4.3‐, and 1.8‐fold faster hydroxylation activity towards phenol, toluene, and naphthalene, respectively, compared to native ToMO. The F176H variant also produced the novel product hydroquinone (61%) from phenol, made twofold more 2‐naphthol from naphthalene (34% vs. 16% by the wild‐type ToMO), and had the regiospecificity of toluene changed from 51% to 73% p‐cresol. The TouA F176N variant had the most para‐hydroxylation capability, forming p‐cresol (92%) from toluene and hydroquinone (82%) from phenol as the major product, whereas native ToMO formed 30% o‐cresol, 19% m‐cresol, and 51% of p‐cresol from toluene and 100% catechol from phenol. For naphthalene oxidation, TouA variant F176S exhibited the largest shift in the product distribution by producing threefold more 2‐naphthol. Among the other F196 variants, F196L produced catechol from phenol two times faster than the wild‐type enzyme. The TouA F196I variant produced twofold less o‐cresol and 19% more p‐cresol from toluene, and the TouA F196A variant produced 62% more 2‐naphthol from naphthalene compared to wild‐type ToMO. Both of these positions have never been studied through the saturation mutagenesis and some of the best substitutions uncovered here have never been predicted and characterized for aromatics hydroxylation. Biotechnol. Bioeng. 2014;111: 1506–1512. © 2014 Wiley Periodicals, Inc.
Subtile Verteidigungsstrategien in Pflanzen
Authors: Mithöfer Axel , Schuman Meredith C. 
Published: February 2014

AbstractPflanzen verteidigen sich gegen herbivore Angriffe sehr effizient durch den Einsatz von Chemie. Neben Verbindungen, die direkt auf den Aggressor wirken, produziert die von pflanzenfressenden Arthropoden befallene Pflanze auch niedermolekulare, flüchtige Stoffe, meistens Terpene und Acetogenine, die an die Umgebung abgegeben werden. Diese wirken als Signalstoffe mit unterschiedlichen Funktionen. So können sie einerseits Räuber oder Parasitoide der nächsthöheren trophischen Ebene anlocken, die die fressenden Herbivoren angreifen und somit die befallenen Pflanzen indirekt verteidigen; andererseits können solche Duftstoffe von benachbarten Teilen derselben Pflanzen wahrgenommen werden. Diese noch unbefallenen Bereiche der Pflanze können sich dann entsprechend wappnen und sind schneller in der Lage, ihre Verteidigung im Bedarfsfall zu aktivieren. Eine Anwendung des Prinzips einer natürlichen pflanzlichen Verteidigung in der Landwirtschaft ist durchaus denkbar.
Hochwasser – ein unterschätztes Risiko
Authors: Hollert Henner , Brinkmann Markus , Hudjetz Sebastian , Cofalla Catrina , Schüttrumpf Holger 
Published: February 2014

AbstractHochwasserereignisse stellen in überschwemmungsgefährdeten Gebieten immer wieder eine Bedrohung für Leben, Gesundheit und Eigentum der Bevölkerung sowie für Industrie, Landwirtschaft und Infrastruktureinrichtungen dar. Problematisch sind dabei aber nicht nur diese eher direkten Auswirkungen: Historische Belastungen – tickende “Zeitbomben” – im Sediment können durch Erosion erneut in die Gewässersäule gelangen. Dort können sie die Gewässerqualität nachhaltig beeinträchtigen und die Gesundheit aquatischer Organismen und auch des Menschen gefährden. In diesem Artikel werden verschiedene Untersuchungen zum Schädigungspotenzial von Hochwassern und speziell die Befunde einer kombinierten hydrologischen und ökotoxikologischen Untersuchungsmethodik vorgestellt.
Domestikation im Zeitraffer: Wie die Gerste zu mehr Körnern kam
Authors: Hensel Götz , Kumlehn Jochen 
Published: February 2014

AbstractWildgerste ist 2‐zeilig, Kulturgerste meist 6‐zeilig und damit ertragreicher. Doch wie kommt diese Zuchtform zu mehr Körnern? Aktuelle Forschungsergebnisse zeigen, dass ein durch das Vrs1‐Gen codierter Transkriptionsfaktor die Entwicklung seitlich positionierter Ährchen unterdrückt, während die 6‐Zeiligkeit auf einer verminderten Genaktivität beruht. Unterdrückt man das Vrs1‐Gen durch RNAi, werden Wildtypen zu Zuchtformen – die Domestikation wird im Schnelldurchlauf nachvollzogen.
Evaluation of fitness levels of children with a diagnosis of acute leukemia and lymphoma after completion of chemotherapy and autologous hematopoietic stem cell transplantation
Authors: Bianco Antonino , Patti Antonino , Thomas Ewan , Palma Romilda , Maggio Maria Cristina , Paoli Antonio , Palma Antonio 
Published: February 2014

AbstractThe aim of this study was to assess the fitness levels and possible deficits in physical performance in children with a diagnosis of childhood acute leukemia and lymphoma after 10 months of therapy ending through a specific test battery. A total of 58 subjects were enrolled in this study. The experimental group (EG) (7.55 ± 2.43 years; 41.8 ± 16.37 kg; 144.6 ± 10.21 cm) consisted of 18 children with diagnosed leukemia and lymphoma after completion of 10 months of therapy intervention and 40 healthy children who were enrolled in a control group (CG) (7.92 ± 1.78 years; 37.4 ± 12.37 kg; 140.6 ± 12.61 cm). A testing battery including the standing broad jump; the sit‐up test; the 4 × 10 m shuttle run test, and the hand grip strength test were administered to both groups. An unpaired t‐test was adopted to determine differences and the Pearson product moment was administered when appropriate. Results of the EG were generally lower when compared to the CG. Significant differences were identified for the standing broad jump (P < 0.05); 4 × 10 m shuttle run (P < 0.05); hand grip test DX (P < 0.05), and hand grip test SX (P < 0.05). No significant differences were found between the sit‐up tests. Pearson product moment correlation revealed a good interaction for all EG participants. Findings suggest that the proposed testing battery could be an appropriate tool to evaluate residual fitness levels in children with previous hematological malignancies. However, our results have to be confirmed with a larger number of participants with the same diagnosis of our EG.
Two BRM promoter insertion polymorphisms increase the risk of early‐stage upper aerodigestive tract cancers
Authors: Wong Kit Man , Qiu Xiaoping , Cheng Dangxiao , Azad Abul Kalam , Habbous Steven , Palepu Prakruthi , Mirshams Maryam , Patel Devalben , Chen Zhuo , Roberts Heidi , Knox Jennifer , Marquez Stephanie , Wong Rebecca , Darling Gail , Waldron John , Goldstein David , Leighl Natasha , Shepherd Frances A. , Tsao Ming , Der Sandy , Reisman David , Liu Geoffrey 
Published: February 2014

AbstractBrahma (BRM) has a key function in chromatin remodeling. Two germline BRM promoter insertion–deletion polymorphisms, BRM‐741 and BRM‐1321, have been previously associated with an increased risk of lung cancer in smokers and head and neck cancer. To further evaluate their role in cancer susceptibility particularly in early disease, we conducted a preplanned case–control study to investigate the association between the BRM promoter variants and stage I/II upper aerodigestive tract (UADT) cancers (i.e., lung, esophageal, head and neck), a group of early‐stage malignancies in which molecular and genetic etiologic factors are poorly understood. The effects of various clinical factors on this association were also studied. We analyzed 562 cases of early‐stage UADT cancers and 993 matched healthy controls. The double homozygous BRM promoter variants were associated with a significantly increased risk of early stage UADT cancers (adjusted odds ratio [aOR], 2.46; 95% confidence interval [CI], 1.7–3.8). This association was observed in lung (aOR, 2.61; 95% CI, 1.5–4.9) and head and neck (aOR, 2.75; 95% CI, 1.4–5.6) cancers, but not significantly in esophageal cancer (aOR, 1.66; 95% CI, 0.7–5.8). There was a nonsignificant trend for increased risk in the heterozygotes or single homozygotes. The relationship between the BRM polymorphisms and early‐stage UADT cancers was independent of age, sex, smoking status, histology, and clinical stage. These findings suggest that the BRM promoter double insertion homozygotes may be associated with an increased risk of early‐stage UADT cancers independent of smoking status and histology, which must be further validated in other populations.
Production of Tailor‐Made Enzymes for Detergents
Authors: Rähse Wilfried 
Published: February 2014

AbstractIncorporated in detergents, special enzymes are able to remove natural stains from laundry at temperatures of 60 °C and below. The various enzymes form complexes with the substrates (stains) and hydrolyze fixed proteins and polysaccharides as well fats. Surfactants rinse the resulting fragments into the wash liquor. The genes for the synthesis of these enzymes, which predominantly originate from Bacillus strains, are optimized for the desired performance of the enzymes. They work nonspecifically and are resistant to the detergent ingredients in the liquor. Industrial production of the enzymes takes place in fermenters 40 to 125 m3 in size. During the fermentation, microorganisms secrete the enzyme into the medium to cleave proteins with high molecular weight, which swim in the broth. The fragments penetrate into the cell and serve as energy source. After the end of fermentation, the enzymes are separated from the microorganisms, concentrated and converted into the final product. Granulated products, containing the enzymes in the matrix, require a coating to ensure product safety. Product design is determined on the one hand by protein engineering and on the other hand by design of the final product.
200 Years in Innovation of Continuous Distillation
Authors: Kockmann Norbert 
Published: February 2014

AbstractDistillation is one of the oldest and most frequently used purification methods today. In 1813, Jean‐Baptiste Cellier‐Blumenthal patented the first continuously working distillation column, starting an impressive development of process equipment. New product areas were discovered as well as improved equipment installations. 100 years ago, Fritz Raschig patented his rings as packing material. Current developments are guided by deeper knowledge of heat and mass transfer as well as the integration of various process functions.
Current Developments in Cellulase Engineering
Authors: Kellermann Stefanie J. , Rentmeister Andrea 
Published: February 2014

AbstractDegradation of cellulose represents a key step for efficient generation of biofuels such as ethanol or butanol from nonfood crops. Several strategies aim to improve the performance of cellulases in order to make the overall process more cost‐efficient.In one strategy, novel arrangements of cellulases are developed. The resulting so‐called designer cellulosomes might allow to equip the fermenting hosts with sufficient cellulase activity to grow on cellulose as sole carbon source and thus enable consolidated bioprocessing.Other strategies aim to engineer cellulases with higher thermostability and activity to make cellulose hydrolysis more efficient. This review summarizes current developments in the field of cellulase engineering and highlight achievements as well as limitations.
Using 15N‐Ammonium to Characterise and Map Potassium Binding Sites in Proteins by NMR Spectroscopy
Authors: Werbeck Nicolas D. , Kirkpatrick John , Reinstein Jochen , Hansen D. Flemming 
Published: February 2014

AbstractA variety of enzymes are activated by the binding of potassium ions. The potassium binding sites of these enzymes are very specific, but ammonium ions can often replace potassium ions in vitro because of their similar ionic radii. In these cases, ammonium can be used as a proxy for potassium to characterise potassium binding sites in enzymes: the 1H,15N spin‐pair of enzyme‐bound 15NH4+ can be probed by 15N‐edited heteronuclear NMR experiments. Here, we demonstrate the use of NMR spectroscopy to characterise binding of ammonium ions to two different enzymes: human histone deacetylase 8 (HDAC8), which is activated allosterically by potassium, and the bacterial Hsp70 homologue DnaK, for which potassium is an integral part of the active site. Ammonium activates both enzymes in a similar way to potassium, thus supporting this non‐invasive approach. Furthermore, we present an approach to map the observed binding site onto the structure of HDAC8. Our method for mapping the binding site is general and does not require chemical shift assignment of the enzyme resonances.
Mafia and psychopathy
Authors: Schimmenti Adriano , Caprì Chiara , La Barbera Daniele , Caretti Vincenzo 
Published: February 2014

ABSTRACTBackgroundIn popular culture, Mafia members are often portrayed as ruthless, callous and remorseless, but there is no empirical research on their personality traits.AimsThe goal of this research was to examine levels of psychopathic traits among Mafia members who have been convicted of a criminal offence.MethodsThe Psychopathy Checklist‐Revised (PCL‐R) rated 30 Italian adult male prisoners who had been convicted for Mafia‐related crimes (86% resident in one 6‐month period) and 39 next adjacent convicted men who were not enrolled in any criminal organisation.ResultsMafia members obtained lower PCL‐R total scores, interpersonal and affective (PCL‐R factor 1) scores and lifestyle scores (factor 2) than the other offenders. Logistic regression analysis showed that lower PCL‐R factor 1 scores with higher factor 2 scores in the absence of a history of substance misuse disorder distinguished Mafia from non‐Mafia offenders. A probability curve confirmed an exponential growth in the probability of classification as a Mafia member in relation to lower PCL‐R factor 1 scores.ConclusionsOur findings bring new hope for resocialisation of convicted Mafia members, because they showed significant antisocial traits but they maintained a capacity for emotional connection and greater likelihood of engaging with training and resocialisation programmes than other imprisoned offenders in Italy. Copyright © 2014 John Wiley & Sons, Ltd.
Association of ischemic stroke, hormone therapy, and right to left shunt in postmenopausal women
Authors: Greep Nancy C. , Liebeskind David S. , Gevorgyan Rubine , Truong Tam , Cua Bennett , Tseng Chi‐Hong , Dodick David W. , Demaerschalk Bart M. , Thaler David E. , Tobis Jonathan M. 
Published: February 2014

BackgroundPostmenopausal hormone therapy (HT) increases the risk of venous thrombosis and ischemic stroke.ObjectivesWe postulated that HT might increase the risk of ischemic stroke by promoting venous clots that travel to the brain through a right to left shunt (RLS).MethodsA total of 2,389 records were studied. After eliminating the premenopausal patients, and those with TIAs and non‐ischemic strokes, the medical records of 1846 postmenopausal women hospitalized at four institutions for ischemic stroke were reviewed to identify those who had undergone an adequate study to assess for RLS. The proportion of women with a shunt in users and non‐users of HT was compared in stroke patients and in a reference population consisting of postmenopausal women undergoing elective cardiac catheterization.ResultsThere were 363 (20%) records that had complete data and were included in the analysis. A shunt was more prevalent in patients with a cryptogenic stroke than in patients with a stroke of known cause (55/88 (63%) vs. 53/275 (19%), P < 0.001). In patients with a stroke of known cause, the frequency of a shunt was similar to that in reference women 31/136 (23%), and the proportion of women with a shunt was similar in non‐users and current users of HT (14% vs. 20%, P = 0.40). However, among patients with a cryptogenic stroke, the prevalence of a shunt was 1.5 times higher in current users than non‐users of HT (82% vs. 56%, P = 0.04).ConclusionsApproximately 23% of older women have a RLS. HT in these women may increase the risk of ischemic stroke by promoting paradoxical embolism. © 2014 Wiley Periodicals, Inc.
Bioreductions Catalyzed by an Alcohol Dehydrogenase in Non‐aqueous Media
Authors: Kara Selin , Spickermann Dominik , Weckbecker Andrea , Leggewie Christian , Arends Isabel W. C. E. , Hollmann Frank 
Published: February 2014

AbstractHighly productive biocatalytic reductions were established using an isolated alcohol dehydrogenase (ADH) under water‐deficient conditions. First, a solvent‐free system was evaluated for the reduction of 2‐butanone catalyzed by ADH evo‐1.1.200 promoted by the “smart cosubstrate” 1,4‐butanediol. ADH evo‐1.1.200 excelled by its activity and stability under high reagent concentrations and hence was the enzyme of choice. However, conversion of 2‐butanone was limited to <1 % in 10 days under the solvent‐free conditions. Therefore, water‐immiscible organic solvents were evaluated whereby the highest conversions were achieved in MTBE and toluene. MTBE was chosen as its different boiling point compared to other reaction components (e.g., 2‐butanone, 2‐butanol, diol cosubstrate, and lactone coproduct) would simplify the downstream processing. Further on, by tuning substrate loading, the productivity of the ADH evo‐1.1.200 was successfully increased to a turnover number (TON) of 64 000.
Identification, Characterization, and Application of Three Enoate Reductases from Pseudomonas putida in In Vitro Enzyme Cascade Reactions
Authors: Peters Christin , Kölzsch Regina , Kadow Maria , Skalden Lilly , Rudroff Florian , Mihovilovic Marko D. , Bornscheuer Uwe T. 
Published: February 2014

AbstractEnoate reductases are versatile enzymes for the enantio‐ and regioselective addition of hydrogen to double bonds. We identified three EREDs (XenA, XenB, NemA) from Pseudomonas putida ATCC 17453 through a sequence motif search. In addition to cloning, functional expression, and biochemical characterization of these enzymes, the enoate reductases were also applied in enzyme cascade reactions in combination with a Baeyer–Villiger monooxygenase and an alcohol dehydrogenase to produce lactones.