bluuebunny/crossref_metadata_2025 huggingface dataset:
The Life and Growth of Language
Authors: Whitney William Dwight
Published: October 2014

William Dwight Whitney (1827–94) was the foremost American philologist and Sanskrit scholar of the nineteenth century. After studying in Germany, then at the forefront of linguistic scholarship, he assumed the chair of Sanskrit at Yale in 1854, with comparative philology added to his professorship in 1869. As well as teaching modern languages, Whitney published over 300 scholarly papers and books, acted as chief editor of the ten-volume Century Dictionary, and co-founded the American Philological Association. In this important 1875 work, the influence of evolutionary theory on other branches of nineteenth-century scholarship, not merely biology, is clear in the discussion of the development of language. Whitney's survey is wide-ranging, beginning with an examination of language acquisition and how language shapes or limits our thought processes. Stressing the scientific basis of historical linguistics, he further looks at how different languages have changed over time, in terms of grammatical form, pronunciation and meaning.
Travels in Kamtschatka
Authors: Lesseps Jean-Baptiste-Barthélemy de
Published: October 2014

Jean-Baptiste-Barthélemy de Lesseps (1766–1834), a French diplomat, served as an interpreter on La Pérouse's voyage around the world, which sailed from Brest in 1785. In 1787, on the eastern coast of the Kamchatka peninsula, he was tasked with an overland mission to get reports back to France as La Pérouse proceeded to Australia. This two-volume work, reissued here in its English translation of 1790, is a compelling account of the one-year journey from Russia to France, and a tale of endurance and resourcefulness in the face of forbidding conditions. More than a mere journal, it also relates the author's observations on the way of life in Kamchatka, its institutions and trade. Rich in detail, the work will appeal to historians and readers with an interest in transcontinental adventure. Volume 1 covers his journey from Petropavlovsk-Kamchatsky to the north-eastern extremity of the Sea of Okhotsk.
Notes on Hospitals
Authors: Nightingale Florence
Published: October 2014

Returning from the Crimea, Florence Nightingale (1820–1910) used her experience of army medicine to ameliorate civilian nursing care. She was appalled by the conditions she found, affirming that the first requirement of a hospital was that 'it should do the sick no harm'. Problems such as overcrowding and damp, in addition to lack of ventilation and proper sanitation, contributed to high mortality rates. Nightingale's belief that such suffering was preventable was seen as revolutionary. In 1859 she published her two most influential works, Notes on Nursing (also reissued in this series) and Notes on Hospitals. This collection contains the two papers she presented to the National Association for the Promotion of Social Science in 1858. Also included, from 1857, is her evidence to the royal commission on the British army's sanitary conditions. Three illustrated articles on hospital design, published in The Builder in 1858, form an appendix to the work.
Popular Instructions on the Calculation of Probabilities
Authors: Quetelet Lambert Adolphe Jacques
Published: October 2014

The Belgian polymath Lambert Adolphe Jacques Quetelet (1796–1874) was regarded by John Maynard Keynes as a 'parent of modern statistical method'. Applying his training in mathematics to the physical and psychological dimensions of individuals, his Treatise on Man (also reissued in this series) identified the 'average man' in statistical terms. Reissued here is the 1839 English translation of his 1828 work, which appeared at a time when the application of probability was moving away from gaming tables towards more useful areas of life. Quetelet believed that probability had more influence on human affairs than had been accepted, and this work marked his move from a focus on mathematics and the natural sciences to the study of statistics and, eventually, the investigation of social phenomena. Written as a summary of lectures given in Brussels, the work was translated from French by the engineer Richard Beamish (1798–1873).
Augustine Deformed
Authors: Rist John M.
Published: October 2014

Augustine established a moral framework that dominated Western culture for more than a thousand years. His partly flawed presentation of some of its key concepts (love, will and freedom), however, prompted subsequent thinkers to attempt to repair this framework, and their efforts often aggravated the very problems they intended to solve. Over time, dissatisfaction with an imperfect Augustinian theology gave way to increasingly secular and eventually impersonal moral systems. This volume traces the distortion of Augustine's thought from the twelfth century to the present and examines its consequent reconstructions. John M. Rist argues that modern philosophies should be recognized as offering no compelling answers to questions about the human condition and as leading inevitably to conventionalism or nihilism. In order to avoid this end, he proposes a return to an updated Augustinian Christianity. Essential reading for anyone interested in Augustine and his influence, Augustine Deformed revitalizes his original conception of love, will and freedom.
Notes of a Twelve Years' Voyage of Discovery in the First Six Books of the Eneis
Authors: Henry James
Published: October 2014

Born in Dublin and classically educated at Trinity College, James Henry (1798–1876) practised as a doctor for more than twenty years before an inheritance allowed him to focus on the close study of Virgil's Aeneid. Travelling extensively across Europe, Henry conferred with eminent scholars and consulted numerous manuscripts. After the death of his wife in 1849, he was accompanied and ably assisted in his quest by his sole surviving daughter, Katherine Olivia (1830–72). In 1853 he published in Dresden his textual analysis of the poem's first six books. Reissued here is the version that appeared in Britain in 1859. This painstaking research was in turn incorporated into Henry's monumental multi-volume commentary, Aeneidea, published between 1873 and 1892 and now also reissued in the Cambridge Library Collection. The present work throws much light on both the ancient text and the approach of an idiosyncratic and indefatigable Virgilian scholar.
Sir Francis Chantrey
Authors: Jones George
Published: October 2014

A painter, army officer and eminent Royal Academician, George Jones (1786–1869) enjoyed a close friendship with the sculptor Sir Francis Chantrey (1781–1841). Britain's portrait sculptor of choice at the peak of his career, Chantrey is most celebrated for works such as his busts of Sir Walter Scott and John Horne Tooke, his statue of James Watt, the equestrian bronze of Sir Thomas Munro in India, and The Sleeping Children in Lichfield Cathedral. Originally published in 1849, this book is an affectionate tribute to the man and his work, featuring also a selection of his letters to Jones, the engraver Charles Turner, and other correspondents. Whereas Jones's patriotism led him to enlist, Chantrey's was reflected in his enthusiasm for the advancement and promotion of his country's art: his generous bequest to the Royal Academy allowed for the purchase of numerous works of British art, now held by the Tate.
The History of a Voyage to the Malouine (or Falkland) Islands
Authors: Pernety Antoine-Joseph
Published: October 2014

After the French and Indian War, in which France and England had fought over the control of North America, the French government decided to send an expedition to the Falkland Islands, or Isles Malouines, with a view to founding a colony where the Acadians expelled from Canada could settle. Under the command of Louis-Antoine de Bougainville (1729–1811), the 1763–4 expedition claimed these islands for France and established a base at Port Saint Louis. This work, translated from French and first published in English in 1771, is an illustrated account of this endeavour by Antoine-Joseph Pernety (1716–96), a naturalist and writer who took part in the expedition. Notably, it contains the first description of the geological phenomena of the stone runs on East Falkland. The latter part of the work is a compilation of letters and notes pertaining to subsequent voyages to Patagonia and the Straits of Magellan.
Philosophy and the Precautionary Principle
Authors: Steel Daniel
Published: October 2014

Scholars in philosophy, law, economics and other fields have widely debated how science, environmental precaution, and economic interests should be balanced in urgent contemporary problems, such as climate change. One controversial focus of these discussions is the precautionary principle, according to which scientific uncertainty should not be a reason for delay in the face of serious threats to the environment or health. While the precautionary principle has been very influential, no generally accepted definition of it exists and critics charge that it is incoherent or hopelessly vague. This book presents and defends an interpretation of the precautionary principle from the perspective of philosophy of science, looking particularly at how it connects to decisions, scientific procedures, and evidence. Through careful analysis of numerous case studies, it shows how this interpretation leads to important insights on scientific uncertainty, intergenerational justice, and the relationship between values and policy-relevant science.
Modernism and the Reinvention of Decadence
Authors: Sherry Vincent
Published: October 2014

In this major new book, Vincent Sherry reveals a fresh continuity in literary history. He traces the idea of decadence back to key events from the failures of the French Revolution to the cataclysm of the Great War. This powerful work of literary criticism and literary history encompasses a rich trajectory that begins with an exposition of the English Romantic poets and ends with a re-evaluation of modernists as varied as W. B. Yeats, Henry James, Joseph Conrad, Rebecca West, Djuna Barnes, Samuel Beckett and, centrally, Ezra Pound and T. S. Eliot. Sherry's hugely ambitious study will be essential reading for anyone working in modernist studies and twentieth-century literature more generally.
Expert Adjustments of Model Forecasts
Authors: Franses Philip Hans
Published: October 2014

To what extent should anybody who has to make model forecasts generated from detailed data analysis adjust their forecasts based on their own intuition? In this book, Philip Hans Franses, one of Europe's leading econometricians, presents the notion that many publicly available forecasts have experienced an 'expert's touch', and questions whether this type of intervention is useful and if a lighter adjustment would be more beneficial. Covering an extensive research area, this accessible book brings together current theoretical insights and new empirical results to examine expert adjustment from an econometric perspective. The author's analysis is based on a range of real forecasts and the datasets upon which the forecasters relied. The various motivations behind experts' modifications are considered, and guidelines for creating more useful and reliable adjusted forecasts are suggested. This book will appeal to academics and practitioners with an interest in forecasting methodology.
VCF2Networks: applying genotype networks to single-nucleotide variants data
Authors: Dall'Olio Giovanni Marco , Vahdati Ali R. , Bertranpetit Jaume , Wagner Andreas , Laayouni Hafid
Published: October 2014

Summary: A wealth of large-scale genome sequencing projects opens the doors to new approaches to study the relationship between genotype and phenotype. One such opportunity is the possibility to apply genotype networks analysis to population genetics data. Genotype networks are a representation of the set of genotypes associated with a single phenotype, and they allow one to estimate properties such as the robustness of the phenotype to mutations, and the ability of its associated genotypes to evolve new adaptations. So far, though, genotype networks analysis has rarely been applied to population genetics data. To help fill this gap, here we present VCF2Networks, a tool to determine and study genotype network structure from single-nucleotide variant data.

Availability and implementation: VCF2Networks is available at https://bitbucket.org/dalloliogm/vcf2networks .

Contact:  giovanni.dallolio@kcl.ac.uk

Supplementary information : Supplementary data are available at Bioinformatics online.
CompMap: a reference-based compression program to speed up read mapping to related reference sequences
Authors: Zhu Zexuan , Li Linsen , Zhang Yongpeng , Yang Yanli , Yang Xiao
Published: October 2014

Summary : Exhaustive mapping of next-generation sequencing data to a set of relevant reference sequences becomes an important task in pathogen discovery and metagenomic classification. However, the runtime and memory usage increase as the number of reference sequences and the repeat content among these sequences increase. In many applications, read mapping time dominates the entire application. We developed CompMap, a reference-based compression program, to speed up this process. CompMap enables the generation of a non-redundant representative sequence for the input sequences. We have demonstrated that reads can be mapped to this representative sequence with a much reduced time and memory usage, and the mapping to the original reference sequences can be recovered with high accuracy.

Availability and implementation : CompMap is implemented in C and freely available at http://csse.szu.edu.cn/staff/zhuzx/CompMap/ .

Contact : xiaoyang@broadinstitute.org

Supplementary information : Supplementary data are available at Bioinformatics online.
Leveraging ancestry to improve causal variant identification in exome sequencing for monogenic disorders
Authors: Brown Robert , Lee Hane , Eskin Ascia , Kichaev Gleb , Lohmueller Kirk E. , Reversade Bruno , Nelson Stanley F. , Pasaniuc Bogdan
Published: October 2014

Recent breakthroughs in exome sequencing technology have made possible the identification of many causal variants of monogenic disorders. Although extremely powerful when closely related individuals (e.g. child and parents) are simultaneously sequenced, exome sequencing of individual only cases is often unsuccessful due to the large number of variants that need to be followed-up for functional validation. Many approaches remove from consideration common variants above a given frequency threshold (e.g. 1%), and then prioritize the remaining variants according to their allele frequency, functional, structural and conservation properties. In this work, we present methods that leverage the genetic structure of different populations while accounting for the finite sample size of the reference panels to improve the variant filtering step. Using simulations and real exome data from individuals with monogenic disorders, we show that our methods significantly reduce the number of variants to be followed-up (e.g. a 36% reduction from an average 418 variants per exome when ancestry is ignored to 267 when ancestry is taken into account for case-only sequenced individuals). Most importantly our proposed approaches are well calibrated with respect to the probability of filtering out a true causal variant (i.e. false negative rate, FNR), whereas existing approaches are susceptible to high FNR when reference panel sizes are limited.
Density‐dependent habitat selection of spawning Chinook salmon: broad‐scale evidence and implications
Authors: Falcy Matthew R.
Published: October 2014

An extensive body of theory suggests that density‐dependent habitat selection drives many fundamental ecological processes. The ideal free distribution and the ideal despotic distribution make contrasting predictions about the effect of total population size on relative abundances among habitats. Empirical assessment of these habitat selection models is uncommon because data must be collected over large temporal and spatial scales.

I ask whether fluctuation in Chinook salmon (Oncorhynchus tshawytscha) spawner population size through time leads to different relative densities over space.

Twenty‐six years of monitoring data on spawning Chinook salmon across the entire coast of Oregon, USA, were used to evaluate models that make contrasting statements about the interactions of a latent population abundance parameter with physical habitat characteristics.

There is strong information‐theoretic support for models that include terms that allow the spatial variation in density to change as population size changes through time. Analysis of the best model reveals nonlinear isodars, which suggests a ‘despotic’ or ‘preemptive’ distribution of individuals across habitats, indicating that dominant or early‐arriving individuals exclude others from breeding sites.

This finding has implications for genetic dynamics, population dynamics and conservation metrics of these highly valued fish. The novel application of modelling techniques used here to assess mechanisms of habitat selection from observational data can be used in the emerging field of eco‐evolutionary dynamics.
Assembly patterns of mixed‐species avian flocks in the Andes
Authors: Colorado Gabriel J. , Rodewald Amanda D.
Published: October 2014

The relative contribution of deterministic and stochastic processes in the assembly of biotic communities is a central issue of controversy in community ecology. However, several studies have shown patterns of species segregation that are consistent with the hypothesis that deterministic factors such as competition and niche‐partitioning structure species assemblages in animal communities.

Community assembly provides a theoretical framework for understanding these processes, but it has been seldom applied to social aggregations within communities.

In this research, we assessed patterns of non‐randomness in Andean mixed‐species flocks using three assembly models: (i) co‐occurrence patterns; (ii) guild proportionality; and (iii) constant body‐size ratios using data from 221 species of resident and Neotropical migrant birds participating in 311 mixed‐species flocks at 13 regions distributed in Venezuela, Colombia, Ecuador and Peru.

Significant assembly patterns for mixed‐species flocks based on co‐occurrence models and guild proportionality models suggest that competitive interactions play an important role in structuring this social system in the Andes. Distribution of species among foraging guilds (i.e. insectivore, frugivore, omnivore, nectivore) was generally similar among flocks, though with some regional variation.

In contrast, we found little evidence that structuring of mixed‐species flocks in the Andes was mediated by body size. Rather, we found greater than expected variance of body‐size ratios within flocks, indicating that birds did not segregate morphologically.

Overall, our findings suggest that deterministic factors associated to competitive interactions are important contributors to mixed‐species flock assemblages across the Andes.
Complete mesocolic excision in colorectal cancer: a systematic review
Authors: Kontovounisios C. , Kinross J. , Tan E. , Brown G. , Rasheed S. , Tekkis P.
Published: October 2014

Aim

Several studies have suggested an increased lymph node yield, reduced locoregional recurrence and increased disease‐free survival after complete mesocolic excision (CME) for colorectal cancer. This review was undertaken to assess the use of CME for colon cancer by evaluating the technique and its clinical outcome.

Method

A literature search of publications was performed using PubMed and Medline. Only studies published in English were included. Studies assessed for quality and data were extracted by two independent reviewers. End‐points included number of lymph nodes per patient, quality of the plane of mesocolic excision, postoperative mortality and morbidity, 5‐year locoregional recurrence and 5‐year cancer‐specific survival.

Results

There were 34 articles comprising 12 retrospective studies, nine prospective studies and 13 original articles including case series, observational studies and editorials. Of the prospective studies, four reported an increased lymph node harvest and a survival benefit. The others reported an improvement in the quality of the specimen as assessed by histopathological examination. Laparoscopic CME has the same oncological outcome as open surgery but completeness of excision during laparoscopy may be compromised for tumours in the transverse colon.

Conclusion

Studies demonstrate that CME removes significantly more tissue around the tumour including maximal lymph node clearance. There is little information on serious adverse events after CME and a long‐term survival benefit has not been proved.
Polypoid stromal lesions of the intestines
Authors: Voltaggio Lysandra , Montgomery Elizabeth
Published: October 2014

Interpretation of intestinal mesenchymal lesions is simplified merely by knowing in which anatomic layer they are usually found. For example, Kaposi sarcoma is detected on mucosal biopsies, whereas inflammatory fibroid polyp is almost always in the submucosa. Gastrointestinal stromal tumours (GIST) are centred generally in the muscularis propria. Schwannomas are essentially always in the muscularis propria. Knowledge of the favoured layer is also most important in interpreting colon biopsies, as many mesenchymal polyps are encountered in the colon. Herein we discuss several mesenchymal lesions and point out some diagnostic pitfalls.
Effects of experimental warming, litter species, and presence of macroinvertebrates on litter decomposition and associated decomposers in a temperate mountain stream
Authors: Ferreira Verónica , Chauvet Eric , Canhoto Cristina
Published: October 2014

Small woodland streams make the majority of water courses in most watersheds. Litter decomposition is a key ecosystem process in these shaded streams, and its response to warming can have profound consequences for food webs and the carbon (C) cycle. However, these responses can be modulated by litter identity and the structure of the detrital food web. Here we report on a manipulative study aiming at evaluating the effects of warming (+2.8 °C), litter identity (chestnut (Castanea sativa) or oak (Quercus robur) litter), and the structure of the detrital food web (presence or absence of macroinvertebrates) on litter decomposition and decomposers in a small, temperate woodland stream. Warming significantly stimulated overall (microbial- + macroinvertebrate-driven) decomposition of oak and microbial-driven decomposition of chestnut. The similar shredder densities at elevated and ambient temperatures suggest that stimulated overall decomposition of oak resulted from increased activity of macroinvertebrate individuals. Stimulated microbial-driven decomposition of chestnut resulted from higher fungal activity with warming. Stimulation of litter decomposition by warming can lead to increases in the amount of C returned to the atmosphere and to a faster disappearance of litter from the benthos, with consequences to the C cycle and aquatic food webs.
The Rocky Mountain Region: Problems of Delimitation and Nomenclature
Authors: Crowley John M.
Published: October 2014

This paper presents a new delimitation of the Rocky Mountain Region and examines some of the major diffferences between it and several well-known delimitations. The author has delimited the Rocky Mountains as a landscape region, that is, a region based on what the landscape looks like. Within the new boundary are the Columbia Mountains of Canada, the Okanogan Highlands of Washington, the Blue Mountains of Oregon, the Spanish Peaks of Colorado, the so-called High Plateaus of Utah, and some other areas that long have been excluded from the Rockies in traditional physiographic delimitations.
Epidemiology of idiopathic inflammatory myopathy in Hungary
Authors: Nagy-Vincze Melinda , Bodoki Levente , Griger Zoltán , Dankó Katalin
Published: October 2014

Introduction: Idiopathic inflammatory myopathy (called also myositis) is a systemic autoimmune disease mainly characterised with proximal muscle weakness. The most frequent subsets are polymyositis and dermatomyositis. The epidemiology of these diseases is not entirely explored. There is a need to build national and international registries which may help to obtain more data. The Myositis Team at the Department of Clinical Immunology, University of Debrecen, has been established in 1975. Aim: The aim of the authors was to obtain epidemiological data on this disease. Method: The authors analysed the database of the National Health Insurance Fund Administration of Hungary which included 1119 patients with myositis, of which 289 patients were followed up by the authors. Results: The average incidence of the disease was found to be 0.95/100.000/year. The male/female ratio was 1/2. Dermatomyositis occurred both in children and adult, but polymyositis was found mainly in adults. These epidemiological data partly correlate with those published in the international literature. Conclusions: The authors propose to establish a National Myositis Registry in the frame of multicentric collaboration in order to have more information about the disease. Orv. Hetil., 2014, 155(41), 1643–1646.
Single Screw Extrusion Processing of Soy White Flakes Based Catla Feed
Authors: Singh Sushil Kumar , Muthukumarappan Kasiviswanathan
Published: October 2014

An initial investigation into the inclusion of soy white flakes (SWF) and high protein distillers dried grains (HP-DDG) in catla (Catla catla) diet, belonging to the family Cyprinidae, was conducted using a single screw extruder. Three isocaloric (302 kcal/100 g) ingredient blends containing graded levels of SWF in combination with HP-DDG and other required ingredients were formulated to contain a net protein content of 31.5% (wet basis). Extrusion processing was then performed using three levels each of SWF content, moisture content, and temperature gradient keeping a constant screw speed and die diameter. Effects of these variables on extrudate physical properties including: color, pellet durability index, bulk density, water absorption index, water solubility index, unit density and expansion ratio were extensively analyzed. Increasing the level of SWF resulted in increase in water absorption index and unit density but decrease in expansion ratio. The interaction effect of SWF content, moisture content and temperature were significant for color, pellet durability index, bulk density and expansion ratio. All the extrudates showed relatively high pellet durability and inclusion of SWF produced less expanded and more compact textured extrudates.
How the physical properties of food influence its selection by infant Japanese macaques inhabiting a snow‐covered area
Authors: Taniguchi Haruka
Published: October 2014

Dietary differences exist between infant and adult female non‐human primates. These differences are considered to be related to the low ability of infants to bite, handle, and obtain food items. This study aimed to provide a comprehensive examination of how the physical properties of food items (fracture toughness, size, processing, and height) influence food selection by infant primates. In this study, four mother–infant Japanese macaque (Macaca fuscata) pairs were investigated in a snow‐covered area during winter. The feeding behavior of both mothers and infants was recorded. The size, need for processing, and height of food items were recorded by direct observation, while the fracture toughness of food items (evaluating the required bite force by incisors) was measured using a rheometer. On average, infants spent 14% less time feeding than their mothers, and there were dietary differences between mothers and infants. Compared to their mothers, infants fed relatively more frequently on food items that were small, at a low position, or that could be consumed without processing. In addition, infants spent less time feeding on food items that were tougher than 2,000 J/m2. Thus, infants fed relatively more frequently on food items that are easy to obtain. This food selection by infants reduced the costs of feeding and allowed them to avoid falling from high trees. Am. J. Primatol. 77:285–295, 2015. © 2014 Wiley Periodicals, Inc.
Fixierung cyclischer Peptide: Mimetika von Proteinstrukturmotiven
Authors: Hill Timothy A. , Shepherd Nicholas E. , Diness Frederik , Fairlie David P.
Published: October 2014

Viele Proteine entfalten ihre biologische Aktivität über kleine exponierte Oberflächenregionen aus gefalteten Peptiden mit wohldefinierten dreidimensionalen Strukturen, Epitope genannt. Kurze synthetische Peptidsequenzen, die diesen bioaktiven Proteinoberflächen entsprechen, bilden in Wasser keine thermodynamisch stabilen proteinähnlichen Strukturen. Die Bildung proteinähnlicher biologisch aktiver Konformationen (Stränge, Helices, Kehren) kann jedoch durch Cyclisierung in Verbindung mit anderen molekularen Verstrebungen induziert werden. Letztere helfen bei der Feinabstimmung der dreidimensionalen Struktur. Solche fixierten cyclischen Peptide können ähnliche biologische Aktivitäten und Wirkungen wie das als Vorbild dienende Protein haben, sodass sie als biologische Sonden und Leitstrukturen für Therapeutika, Diagnostika und Impfstoffe dienen können. Dieser Aufsatz beleuchtet Beispiele für cyclische Peptide, die dreidimensionale Strukturen von Strang‐, Kehren‐ oder Helixabschnitten von Peptiden und Proteinen nachahmen und beschreibt einige weitere Elemente, die in cyclisch peptidischen Naturstoffen und synthetischen makrocyclischen Peptidomimetika vorkommen, dort die Peptidstruktur verfeinern und ihr biologische Aktivitäten verleihen.
Enantioselective Iron‐Catalyzed Intramolecular Cyclopropanation Reactions
Authors: Shen Jun‐Jie , Zhu Shou‐Fei , Cai Yan , Xu Huan , Xie Xiu‐Lan , Zhou Qi‐Lin
Published: October 2014

An iron‐catalyzed asymmetric intramolecular cyclopropanation was realized in high yields and excellent enantioselectivity (up to 97 % ee) by using the iron complexes of chiral spiro‐bisoxazoline ligands as catalysts. The superiority of iron catalysts exhibited in this reaction demonstrated the potential abilities of this sustainable metal in asymmetric carbenoid transformation reactions.
Isolation of an Imino‐N‐heterocyclic Carbene/Germanium(0) Adduct: A Mesoionic Germylene Equivalent
Authors: Su Bochao , Ganguly Rakesh , Li Yongxin , Kinjo Rei
Published: October 2014

An autoionization of germanium dichloride/dioxane complex with an imino‐N‐heterocyclic carbene ligand (L) afforded a novel germyliumylidene ion, [(L)GeCl]+[GeCl3]−, which was fully characterized. Reduction of the germyliumylidene ion with potassium graphite produced a cyclic species [(L)Ge], which can be viewed as both a Ge0 species and a mesoionic germylene. X‐ray diffraction analysis and computational studies revealed one of the lone pairs on the Ge atom is involved in the π system on the GeC2N2 five‐membered ring. It was also confirmed that the nucleophilic behavior of [(L)Ge] as a two lone‐pair donor.
B(C6F5)3‐Catalyzed Hydrogenation of Oxime Ethers without Cleavage of the NO Bond
Authors: Mohr Jens , Oestreich Martin
Published: October 2014

The hydrogenation of oximes and oxime ethers is usually hampered by NO bond cleavage, hence affording amines rather than hydroxylamines. The boron Lewis acid B(C6F5)3 is found to catalyze the chemoselective hydrogenation of oxime ethers at elevated or even room temperature under 100 bar dihydrogen pressure. The use of the triisopropylsilyl group as a protecting group allows for facile liberation of the free hydroxylamines.
Zeolites with Continuously Tuneable Porosity
Authors: Wheatley Paul S. , Chlubná‐Eliášová Pavla , Greer Heather , Zhou Wuzong , Seymour Valerie R. , Dawson Daniel M. , Ashbrook Sharon E. , Pinar Ana B. , McCusker Lynne B. , Opanasenko Maksym , Čejka Jiří , Morris Russell E.
Published: October 2014

Zeolites are important materials whose utility in industry depends on the nature of their porous structure. Control over microporosity is therefore a vitally important target. Unfortunately, traditional methods for controlling porosity, in particular the use of organic structure‐directing agents, are relatively coarse and provide almost no opportunity to tune the porosity as required. Here we show how zeolites with a continuously tuneable surface area and micropore volume over a wide range can be prepared. This means that a particular surface area or micropore volume can be precisely tuned. The range of porosity we can target covers the whole range of useful zeolite porosity: from small pores consisting of 8‐rings all the way to extra‐large pores consisting of 14‐rings.
Total Synthesis of (−)‐Haouamine B Pentaacetate and Structural Revision of Haouamine B
Authors: Momoi Yuichi , Okuyama Kei‐ichiro , Toya Hiroki , Sugimoto Kenji , Okano Kentaro , Tokuyama Hidetoshi
Published: October 2014

The enantiocontrolled total synthesis of (−)‐haouamine B pentaacetate was accomplished via an optically active indane‐fused β‐lactam, which was prepared by a newly developed Friedel–Crafts reaction. Subsequent cleavage of the β‐lactam and an intramolecular McMurry coupling reaction provided the core indane‐fused tetrahydropyridine, which led to the elucidation of the structure, as proposed by Trauner and Zubía.
Palladium‐Catalyzed Cross‐Coupling of Styrenes with Aryl Methyl Ketones in Ionic Liquids: Direct Access to Cyclopropanes
Authors: Cotugno Pietro , Monopoli Antonio , Ciminale Francesco , Milella Antonella , Nacci Angelo
Published: October 2014

The combined use of Pd(OAc)2, Cu(OAc)2, and dioxygen in molten tetrabutylammonium acetate (TBAA) promotes an unusual cyclopropanation reaction between aryl methyl ketones and styrenes. The process is a dehydrogenative cyclizing coupling that involves a twofold CH activation at the α‐position of the ketone. The substrate scope highlights the flexibility of the catalyst; a reaction mechanism is also proposed.
Composite Aromatic Boxes for Enzymatic Transformations of Quaternary Ammonium Substrates
Authors: Nagy Gergely N. , Marton Lívia , Contet Alicia , Ozohanics Olivér , Ardelean Laura‐Mihaela , Révész Ágnes , Vékey Károly , Irimie Florin Dan , Vial Henri , Cerdan Rachel , Vértessy Beáta G.
Published: October 2014

Cation–π interactions to cognate ligands in enzymes have key roles in ligand binding and enzymatic catalysis. We have deciphered the key functional role of both charged and aromatic residues within the choline binding subsite of CTP:phosphocholine cytidylyltransferase and choline kinase from Plasmodium falciparum. Comparison of quaternary ammonium binding site structures revealed a general composite aromatic box pattern of enzyme recognition sites, well distinguished from the aromatic box recognition site of receptors.
Direct Mass Spectrometry Analysis of Biofluid Samples Using Slug‐Flow Microextraction Nano‐Electrospray Ionization
Authors: Ren Yue , McLuckey Morgan N. , Liu Jiangjiang , Ouyang Zheng
Published: October 2014

Direct mass spectrometry (MS) analysis of biofluids with simple procedures represents a key step in the translation of MS techniques to clinical and point‐of‐care applications. The current study reports the development of a single‐step method using slug‐flow microextraction and nano‐electrospray ionization for MS analysis of organic compounds in blood and urine. High sensitivity and quantitation precision have been achieved in the analysis of therapeutic and illicit drugs in 5 μL samples. Real‐time chemical derivatization has been incorporated for analyzing anabolic steroids. The monitoring of enzymatic functions has also been demonstrated with cholinesterase in wet blood. The reported study encourages the future development of disposable cartridges, which function with simple operation to replace the traditional complex laboratory procedures for MS analysis of biological samples.
β‐Functionalization of Carboxylic Anhydrides with β‐Alkyl Substituents through Carbene Organocatalysis
Authors: Jin Zhichao , Chen Shaojin , Wang Yuhuang , Zheng Pengcheng , Yang Song , Chi Yonggui Robin
Published: October 2014

The first NHC‐catalyzed functionalization of carboxylic anhydrides is described. In this reaction, the β carbon behaves as a nucleophilic carbon and undergoes asymmetric reactions with electrophiles. Anhydrides with challenging β‐alkyl substituents work effectively.
Control of Regioselectivity over Gold Nanocrystals of Different Surfaces for the Synthesis of 1,4‐Disubstituted Triazole through the Click Reaction
Authors: Rej Sourav , Chanda Kaushik , Chiu Chun‐Ya , Huang Michael H.
Published: October 2014

Gold nanocubes, octahedra, and rhombic dodecahedra were examined for facet‐dependent catalytic activity in the formation of triazoles. Rhombic dodecahedra gave 100 % regioselective 1,4‐triazoles. The product yield was increased by decreasing the particle size. However, a mixture of 1,4‐ and 1,5‐triazoles was obtained in lower yields when cubes and octahedra of similar sizes were used. The lowest Au‐atom density on the {110} surface and largest unsaturated coordination number of surface Au atoms may explain their best catalytic efficiency and product regioselectivity. Various spectroscopic techniques were employed to verify the formation of the Au–acetylide intermediate and establish the reaction mechanism, in which phenylacetylene binds to the Au {110} surface through the terminal‐binding mode to result in the exclusive formation of 1,4‐triazoles. The smallest rhombic dodecahedra can give diverse 1,4‐disubstituted triazoles in good yields by coupling a wide variety of alkynes and organic halides.
Chemical Preparation of Graphene Materials Results in Extensive Unintentional Doping with Heteroatoms and Metals
Authors: Chua Chun Kiang , Ambrosi Adriano , Sofer Zdeněk , Macková Anna , Havránek Vladimír , Tomandl Ivo , Pumera Martin
Published: October 2014

Chemical synthesis of graphene relies on the usage of various chemical reagents. The initial synthesis step, in which graphite is oxidized to graphite oxide, is achieved by a combination of chemical oxidants and acids. A subsequent chemical reduction step eliminates/reduces most oxygen functionalities to yield graphene. We demonstrate here that these chemical treatments significantly contaminate graphene with heteroatoms/metals, depending on the procedures followed. Contaminations with heteroatoms (N, B, Cl, S) or metals (Mn, Al) were present at relatively high concentrations (up to 3 at %), with their chemical states dependent on the procedures. Such unintentional contaminations (unwanted doping) during chemical synthesis are rarely anticipated and reported, although the heteroatoms/metals may alter the electronic and catalytic properties of graphene. In fact, the levels of unintentionally introduced contaminants on graphene are often higher than typical levels found on intentionally doped graphene. Our findings are important for scientists applying chemical methods to prepare graphene.
Chemical Modification and Energetically Favorable Atomic Disorder of a Layered Thermoelectric Material TmCuTe2 Leading to High Performance
Authors: Lin Hua , Chen Hong , Shen Jin‐Ni , Chen Ling , Wu Li‐Ming
Published: October 2014

Thermoelectric (TE) materials have continuously attracted interest worldwide owing to their capability of converting heat into electricity. However, discovery and design of new TE material system remains one of the greatest difficulties. A TE material, TmCuTe2, has been designed by a substructure approach and successfully synthesized. The structure mainly features CuTe4‐based layers stacking along the c axis that are separated by Tm3+ cations. Such an intrinsic Cu site vacancy structure undergoes a first‐order phase transition at around 606 K driven by the energetically favorable uniform Cu atom re‐distribution on the covalent CuTe4‐based layer substructure, as shown by crystal structure simulations and variable‐temperature XRD data. Featured with very low thermal conductivity (ca. 0.6 W m−1 K−1), large Seebeck coefficient (+185 μV K−1), and moderate electrical conductivity (220 S cm−1), TmCuTe2 has a maximum ZT of 0.81 at 745 K, which is nine times higher than the value of 0.09 for binary Cu2Te, thus making it a promising candidate for mid‐temperature TE applications. Theoretical studies uncover the electronic structure modifications from the metallic Cu2Te to the narrow gap semiconductor TmCuTe2 that lead to such a remarkable performance enhancement.
Functionalized Membranes for Photocatalytic Hydrogen Production
Authors: Troppmann Stefan , König Burkhard
Published: October 2014

Functionalized vesicles for photocatalytic hydrogen production in water have been prepared by co‐embedding of amphiphilic photosensitizers and a hydrogen‐evolving catalyst in phospholipid membranes. The self‐assembly allows a simple two‐dimensional arrangement of the multicomponent system with close spatial proximity, which gave turnover numbers up to 165 for the incorporated amphiphilic cobaloxime water reduction catalyst 3 b under optimized conditions in purely aqueous solution. Superior photocatalytic activity in fluid membranes indicates that mobility and dynamic reorganization of catalytic subunits in the membrane promote the visible‐light‐driven hydrogen production. The functionalized membranes represent nanostructured assemblies for hydrogen production in aqueous solution mimicking natural photosynthesis.
Phosphinothiolates as Ligands for Polyhydrido Copper Nanoclusters
Authors: Huertos Miguel A. , Cano Israel , Bandeira Nuno A. G. , Benet‐Buchholz Jordi , Bo Carles , van Leeuwen Piet W. N. M.
Published: October 2014

The reaction of [CuI(HSC6H4PPh2)]2 with NaBH4 in CH2Cl2/EtOH led to air‐ and moisture‐stable copper hydride nanoparticles (CuNPs) containing phosphinothiolates as new ligands, one of which was isolated by crystallization. The X‐ray crystal structure of [Cu18H7L10I] (L=−S(C6H4)PPh2) shows unprecedented features in its 28‐atom framework (18 Cu and 10 S atoms). Seven hydrogen atoms, in hydride form, are needed for charge balance and were located by density functional theory methods. H2 was released from the copper hydride nanoparticles by thermolysis and visible light irradiation.
Iridium(I)‐Catalyzed Regioselective CH Activation and Hydrogen‐Isotope Exchange of Non‐aromatic Unsaturated Functionality
Authors: Kerr William J. , Mudd Richard J. , Paterson Laura C. , Brown Jack A.
Published: October 2014

Isotopic labelling is a key technology of increasing importance for the investigation of new CH activation and functionalization techniques, as well as in the construction of labelled molecules for use within both organic synthesis and drug discovery. Herein, we report for the first time selective iridium‐catalyzed CH activation and hydrogen‐isotope exchange at the β‐position of unsaturated organic compounds. The use of our highly active [Ir(cod)(IMes)(PPh3)][PF6] (cod=1,5‐cyclooctadiene) catalyst, under mild reaction conditions, allows the regioselective β‐activation and labelling of a range of α,β‐unsaturated compounds with differing steric and electronic properties. This new process delivers high levels of isotope incorporation over short reaction times by using low levels of catalyst loading.
Direct Catalytic Addition of Alkylnitriles to Aldehydes by Transition‐Metal/NHC Complexes
Authors: Sureshkumar Devarajulu , Ganesh Venkataraman , Kumagai Naoya , Shibasaki Masakatsu
Published: October 2014

Invited for the cover of this issue is the group of Masakatsu Shibasaki at the Institute of Microbial Chemistry (BIKAKEN), Tokyo. The image depicts an arsenal of alkylnitriles as highly useful and readily available nucleophiles. Read the full text of the article at 10.1002/chem.201404808.
Water Confined in the Local Field of Ions
Authors: Kojić Dušan , Tsenkova Roumiana , Tomobe Katsufumi , Yasuoka Kenji , Yasui Masato
Published: October 2014

Interionic distances are shorter in concentrated ionic solutions, thus instigating the interaction and overlap of hydration shells, as ions become separated by only one or two layers of water molecules. The simultaneous interaction of water with two oppositely charged ions has, so far, only been investigated by computer simulation studies, because the isolated vibrational spectroscopic signature of these molecules remains undetected. Our combined near‐infrared spectroscopic and molecular dynamics simulation studies of alkali halide solutions present a distinct spectral feature, which is highly responsive to depletion of bulk water and merging of hydration shells. The analysis of this spectral feature demonstrates that absorption trends are in good agreement with the law of matching affinities, thus providing the first successful vibrational spectroscopic treatment of this topic. Combined with commonly observed near‐infrared bands, this feature provides a spectral pattern that describes some relevant aspects of ionic hydration.
Minimally invasive surgery of neuroblastic tumors in children: Indications depend on anatomical location and image‐defined risk factors
Authors: Irtan Sabine , Brisse Hervé J. , Minard‐Colin Véronique , Schleiermacher Gudrun , Canale Sandra , Sarnacki Sabine
Published: October 2014

Background

Minimally invasive surgery (MIS) is still not a well‐accepted surgical approach to remove neuroblastic tumors. We aimed to assess the indications and limits of MIS in this childhood tumor according to tumor location and image‐defined risk factors (IDRFs).

Procedure

Between 2006 and 2012, 39 patients underwent MIS for neuroblastic tumors, using thoracoscopic (n = 20), retroperitoneoscopic (n = 1) or laparoscopic approaches (n = 18). The tumor locations were paravertebral (n = 18; thoracic n = 15, lumbar n = 3), perivascular (n = 5; abdominal n = 2; thoracic n = 3), adrenal (n = 13), pleural (n = 2) and pelvic (n = 1). Two patients were treated for relapses. According to the INRG staging system, IDRFs were absent in 20 patients and present in 19 patients. Ten patients received chemotherapy preoperatively. Mean largest diameter was 35 mm for thoracic tumors (range: 7–85 mm) and 34 mm for abdominal tumors (range: 10–75 mm). Mean follow‐up was 25 months (range: 5–116 months).

Results

Resection was macroscopically incomplete (R2) for six thoracic tumors and one adrenal tumor. Conversion was necessary for three thoracic L2 tumors. Postoperative complications consisted of chylothorax in three patients with L2 paravertebral thoracic tumors, Horner's syndrome in a patient with a cervicothoracic tumor, and renal atrophy in a patient with a L2 abdominal tumor. No perioperative or postoperative complications occurred in patients with adrenal and abdominal paravertebral tumors. The overall survival rate was 98%.

Conclusion

In carefully selected cases, MIS permits safe and efficient resection of neuroblastic tumors in children. Open surgical approach should be considered if organ or vascular control or quality of resection is jeopardized. Pediatr Blood Cancer 2015;62:257–261. © 2014 Wiley Periodicals, Inc.