bluuebunny/crossref_metadata_2025 huggingface dataset:
Jorge Mario Bergoglio and Abraham Skorka. On Heaven and Earth: Pope Francis on Faith, Family, and the Church in the Twenty-First Century
Authors: Ruiz Jean-Pierre
Published: October 2014

No abstract is available.
Holger M. Zellentin. Rabbinic Parodies of Jewish and Christian Literature
Authors: Spielman Loren R.
Published: October 2014

No abstract is available.
Neta Stahl. Jesus among the Jews: Representation and Thought
Authors: Crossley James
Published: October 2014

No abstract is available.
Présentation
Authors: Parent Frédéric
Published: October 2014

Avocat de formation, traducteur de profession et sociologue à temps partiel, Léon Gérin a durablement marqué l’histoire de la sociologie d’ici. Reconnu comme le fondateur de la sociologie canadienne, il a laissé une oeuvre imposante et diversifiée, objet privilégié pour réfléchir aux conditions sociales d’émergence et de développement de la pensée sociologique aux 19e et 20e siècles. Ses écrits intéresseront aussi les chercheurs en sciences sociales préoccupés par l’épreuve empirique du réel et l’articulation entre l’expérience et le sens de la vie en société. Soulignant le 150e anniversaire de naissance du pionnier des études monographiques ou ethnographiques au Québec, ce texte introductif propose une réflexion générale sur la démarche scientifique de la sociologie du triple point de vue de l’enjeu social de connaissance (l’énigme du réel), de la définition de l’objet disciplinaire et de l’élaboration d’une théorie de la connaissance sociologique. Nous présentons en terminant les articles du numéro qui abordent tous, d’une manière ou d’une autre, ces trois aspects de la constitution de la sociologie.
Loss of geosynchronous relativistic electrons by EMIC wave scattering under quiet geomagnetic conditions
Authors: Hyun K. , Kim K.‐H. , Lee E. , Kwon H.‐J. , Lee D.‐H. , Jin H.
Published: October 2014

We have examined relativistic electron flux losses at geosynchronous orbit under quiet geomagnetic conditions. One 3 day period, from 11 to 13 October 2007, was chosen for analysis because geomagnetic conditions were very quiet (3 day average of Kp< 1), and significant losses of geosynchronous relativistic electrons were observed. During this interval, there was no geomagnetic storm activity. Thus, the loss processes associated with geomagnetic field modulations caused by ring current buildup can be excluded. The >2 MeV electron flux at geosynchronous orbit shows typical diurnal variations with a maximum near noon and a minimum near midnight for each day. The flux level of the daily variation significantly decreased from first day to third day for the 3 day period by a factor of >10. The total magnetic field strength (BT) of the daily variation on the third day, however, is comparable to that on the first day. Unlike electron flux decreases, the flux of protons with energies between 0.8 and 4 MeV adiabatically responses to the daily variation of BT. That is, there is no significant decrease of the proton flux when the electron flux decreases. During the interval of quiet geomagnetic conditions, well‐defined electromagnetic ion cyclotron (EMIC) waves were detected at geosynchronous spacecraft. Low‐altitude polar‐orbiting spacecraft observed the precipitation of energetic protons and relativistic electrons in the interval of EMIC waves enhancement. From these observations, we suggest that the EMIC waves at geosynchronous orbit cause pitch angle scattering and relativistic electron losses to the atmosphere under quiet geomagnetic conditions.
Adolescent gang involvement: The role of individual, family, peer, and school factors in a multilevel perspective
Authors: Lenzi Michela , Sharkey Jill , Vieno Alessio , Mayworm Ashley , Dougherty Danielle , Nylund‐Gibson Karen
Published: October 2014

Youth gang involvement is a serious public health challenge as adolescents involved in gangs are more likely than others to engage in violence and aggression. To better understand gang involvement, we examined the role of protective (empathy and parental support) and risk (peer deviance and lack of safety at school) factors, as well as their interactions, in predicting adolescent gang affiliation. The study involved a sample of 26,232 students (53.4% females; mean age = 14.62,SD = 1.69) participating in the California Healthy Kids Survey (CHKS), a survey investigating a wide range of youth health and risk behaviors administered in all California schools every 2 years. Using hierarchical linear modeling (HLM), findings indicated that high levels of empathy and parental support were associated with a lower likelihood of affiliating with a gang. Associating with deviant peers and perceiving the school as unsafe were positively correlated with gang membership. At the school level, lack of safety and type of school (special education, vocational, or alternative school vs. comprehensive schools) were associated with greater probability of gang membership. Empathy mitigated the association between deviant peers and gang membership. Aggr. Behav. 41:386–397, 2015. © 2014 Wiley Periodicals, Inc.
Directed Electric Field Z‐Alignment Kinetics of Anisotropic Nanoparticles for Enhanced Ionic Conductivity
Authors: Batra Saurabh , Unsal Emre , Cakmak Miko
Published: October 2014

In this study, the fast transient evolution of the electric field assisted thickness Z‐direction orientation and assembly of clay particles is studied using a instrumented real time system that simultaneously measures in‐plane and out of plane birefringence. The optical anisotropy master curves are developed, connecting the exposure time and electric field strength with orientation, using a superposition principle. Z‐oriented nanocomposite films manufactured through the R2R process show enhancement through thickness ionic conductivity, useful for membranes of batteries and fuel cells.
An improved methodology for outlier detection in dynamic datasets
Authors: Xu Shu , Baldea Michael , Edgar Thomas F. , Wojsznis Willy , Blevins Terrence , Nixon Mark
Published: October 2014

A time series Kalman filter (TSKF) is proposed that successfully handles outlier detection in dynamic systems, where normal process changes often mask the existence of outliers. The TSKF method combines a time series model fitting procedure with a modified Kalman filter to deal with additive outlier and innovational outlier detection problems in dynamic process dataset. Compared with current outlier detection methods, the new method enjoys the following advantages: (a) no prior knowledge of the process model is needed; (b) it is easy to tune; (c) it can be applied to both univariate and multivariate outlier detection; (d) it is applicable to both on‐line and off‐line operation; (e) it cleans outliers while maintains the integrity of the original dataset. © 2014 American Institute of Chemical EngineersAIChE J, 61: 419–433, 2015
Modeling of continuous self‐classifying spiral jet mills part 2: Powder‐dependent parameters from characterization experiments
Authors: Starkey Derek , Taylor Cathy , Siddabathuni Sunil , Parikh Jinit , Svoronos Spyros , Mecholsky John , Powers Kevin , Iacocca Ron
Published: October 2014

The milling model described in Part 1 has been expanded to a three‐level model with the addition of powder‐dependent parameter function models with simple material characterization measurements as inputs. This allows the determination of these parameters with minimal consumption of powder. Specifically, the powder‐dependent parameters are related to material hardness from microindentation or to a breakage measure from single‐impact milling. Three crystalline powders, sodium bicarbonate, lactose monohydrate, and sucrose, have been used to test the described material characterization techniques and expanded milling model. © 2014 American Institute of Chemical Engineers AIChE J 60: 4096–4103, 2014
Secular trends in physical fitness of Mozambican school‐aged children and adolescents
Authors: Dos Santos Fernanda Karina , Prista António , Gomes Thayse Natacha Queiroz Ferreira , Daca Timóteo , Madeira Aspacia , Katzmarzyk Peter T. , Maia José António Ribeiro
Published: October 2014

Objective

This study presents information about secular trends in physical fitness (PF) levels among Mozambican youth.

Methods

The sample comprises 3,851 subjects (1,791 boys; 2,060 girls) aged 8–15 years who were evaluated at three time points (1992, 1999, 2012). PF tests included handgrip strength, 10 m × 5 m shuttle‐run, sit‐and‐reach, and 1‐mile run/walk. Biological maturity was assessed by sexual characteristics, and percentage body fat was predicted using triceps and subscapular skinfolds. ANCOVA (controlling for age, maturity status, and percentage body fat) was used to compare mean differences in PF tests among the three time points, by sex.

Results

Children in 1992 were more flexible than those from 2012; boys handgrip strength increased from 1992 to 2012, while girls decreased their handgrip strength; youth in 1992 were faster and more agile than their 2012 peers; and a decrease was observed in cardiorespiratory fitness between 1992 and 1999 and between 1992 and 2012 for both sexes.

Conclusions

A negative secular trend among Mozambican children's PF was observed over the last two decades, suggesting that socio‐political, educational, and economical changes occurring during this period had a relevant effect on their PF. This negative trend suggests that development of intervention programs/strategies to improve PF among youth is warranted. Am. J. Hum. Biol. 27:201–206, 2015. © 2014 Wiley Periodicals, Inc.
The digit ratio (2D:4D) in China: A meta‐analysis
Authors: Xu Yin , Zheng Yong
Published: October 2014

Objectives

To explore the 2D:4D in China (mainland and Taiwan) and to analyze the influences of ethnicity, digit measurement methods, age, and latitude on Chinese 2D:4D.

Methods

We here conducted a meta‐analysis of the results of 28 studies. A total of 112 independent samples and 19,093 participants were included.

Results

The sex difference in left 2D:4D only approached significance when outliers were removed (P = 0.078), whereas the right 2D:4D was significantly lower in males compared to females, showing that the magnitude of sex difference was greater for the right hand than for the left hand. No significant differences were found in the 2D:4D between Han and ethnic minorities. The 2D:4D of samples measured using indirect digit measurement tended to be lower than in samples measured using direct digit measurement. Moreover, there were no effects of age and latitude on the 2D:4D in China.

Conclusions

We concluded that the sex differences in Chinese 2D:4D are consistent with the results from western studies, and that genetic pool differences rather than latitude‐related environmental variables affect the 2D:4D in China. In addition, 2D:4D measurements obtained by different digit measurement techniques should not be combined within one study, or used together in comparative studies. Am. J. Hum. Biol. 27:304–309, 2015. © 2014 Wiley Periodicals, Inc.
UBE2A deficiency syndrome: A report of two unrelated cases with large Xq24 deletions encompassing UBE2A gene
Authors: Thunstrom Sofia , Sodermark Liv , Ivarsson Liz , Samuelsson Lena , Stefanova Margarita
Published: October 2014

Intragenic mutations of the UBE2A gene, as well as larger deletions of Xq24 encompassing UBE2A have in recent years been associated with a syndromic form of X‐linked intellectual disability called UBE2A deficiency syndrome or X‐linked intellectual disability type Nascimento (OMIM#300860). Common clinical features in these patients include moderate to severe intellectual disability (ID), heart defects, dysmorphic features such as high forehead, synophrys, prominent supraorbital ridges, almond‐shaped and deep‐set eyes, wide mouth, myxedematous appearance, hirsutism, onychodystrophy, and genital anomalies. This study investigates clinical and molecular data of two unrelated, affected males with chromosome Xq24 deletions encompassing UBE2A. Both have been followed from birth until two years of age. A review of the previously published patients with deletions encompassing UBE2A is provided. Besides the common features, the two boys show anomalies not previously described, such as retinal coloboma, esophageal atresia with esophageal fistula, long fingers, camptodactyly, clinodactyly, and long broad toes. Analyses of the phenotype–genotype correlations suggest considerable prevalence of heart defects in the group of patients with larger deletions of Xq24 in comparison to the patients having intragenic UBE2A mutations. However, further studies are needed in order to establish statistically reliable phenotype–genotype correlations of this syndrome. © 2014 Wiley Periodicals, Inc.
Morphological relationship between the cranial and supraorbital regions in Homo sapiens
Authors: Nowaczewska Wioletta , Kuźmiński Łukasz , Biecek Przemysław
Published: October 2014

Although some hypotheses that attempt to explain the variation in supraorbital region morphology in modern humans have been proposed, this issue is still not well understood. In this study, the craniofacial size and spatial models were tested using a sample of modern human crania from geographically diverse populations, and the co‐occurrence of the degrees of glabella (GL) and superciliary arch (ST) expression were analyzed. The two supraorbital structures were examined by visual assessment, and eight quantitative variables were included in the three‐way ANOVA, canonical variates analysis and partial rank correlation. The influences of sex and the region of origin of the cranial samples on the relationships between the examined variables and the degrees of supraorbital structures expression were also considered. The results only partially supported the craniofacial size and spatial models and suggested that GL and ST experienced separate influences during development. In the sample of all crania, the neurocranial size more strongly influenced the morphological variation of the ST than of the GL, and sex influenced both of these structures the most. The results suggest that sex may be the main factor (having an influence independent of the other traits) on the morphological variation of the GL and ST. Am J Phys Anthropol 156:110–124, 2015 © 2014 Wiley Periodicals, Inc.
Reversible Ca2+ Switch of An Engineered Allosteric Antioxidant Selenoenzyme
Authors: Zhang Chunqiu , Pan Tiezheng , Salesse Christian , Zhang Dongmei , Miao Lu , Wang Liang , Gao Yuzhou , Xu Jiayun , Dong Zeyuan , Luo Quan , Liu Junqiu
Published: October 2014

A Ca2+‐responsive artificial selenoenzyme was constructed by computational design and engineering of recoverin with the active center of glutathione peroxidase (GPx). By combining the recognition capacity for the glutathione (GSH) substrate and the steric orientation of the catalytic selenium moiety, the engineered selenium‐containing recoverin exhibits high GPx activity for the catalyzed reduction of H2O2 by glutathione (GSH). Moreover, the engineered selenoenzyme can be switched on/off by Ca2+‐induced allosterism of the protein recoverin. This artificial selenoenzyme also displays excellent antioxidant ability when it was evaluated using a mitochondrial oxidative damage model, showing great potential for controlled catalysis in biomedical applications.
Reactive Oxygen Species‐Responsive Protein Modification and Its Intracellular Delivery for Targeted Cancer Therapy
Authors: Wang Ming , Sun Shuo , Neufeld Caleb I. , Perez‐Ramirez Bernardo , Xu Qiaobing
Published: October 2014

Herein we report a convenient chemical approach to reversibly modulate protein (RNase A) function and develop a protein that is responsive to reactive oxygen species (ROS) for targeted cancer therapy. The conjugation of RNase A with 4‐nitrophenyl 4‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl) benzyl carbonate (NBC) blocks protein lysine and temporarily deactivates the protein. However, the treatment of RNase A–NBC with hydrogen peroxide (one major intracellular ROS) efficiently cleaves the NBC conjugation and restores the RNase A activity. Thus, RNase A–NBC can be reactivated inside tumor cells by high levels of intracellular ROS, thereby restoring the cytotoxicity of RNase A for cancer therapy. Due to higher ROS levels inside tumor cells compared to healthy cells, and the resulting different levels of RNase A–NBC reactivation, RNase A–NBC shows a significant specific cytotoxicity against tumor cells.
Constraining Cyclic Peptides To Mimic Protein Structure Motifs
Authors: Hill Timothy A. , Shepherd Nicholas E. , Diness Frederik , Fairlie David P.
Published: October 2014

Many proteins exert their biological activities through small exposed surface regions called epitopes that are folded peptides of well‐defined three‐dimensional structures. Short synthetic peptide sequences corresponding to these bioactive protein surfaces do not form thermodynamically stable protein‐like structures in water. However, short peptides can be induced to fold into protein‐like bioactive conformations (strands, helices, turns) by cyclization, in conjunction with the use of other molecular constraints, that helps to fine‐tune three‐dimensional structure. Such constrained cyclic peptides can have protein‐like biological activities and potencies, enabling their uses as biological probes and leads to therapeutics, diagnostics and vaccines. This Review highlights examples of cyclic peptides that mimic three‐dimensional structures of strand, turn or helical segments of peptides and proteins, and identifies some additional restraints incorporated into natural product cyclic peptides and synthetic macrocyclic peptidomimetics that refine peptide structure and confer biological properties.
Cascade Multicomponent Synthesis of Indoles, Pyrazoles, and Pyridazinones by Functionalization of Alkenes
Authors: Matcha Kiran , Antonchick Andrey P.
Published: October 2014

The development of multicomponent reactions for indole synthesis is demanding and has hardly been explored. The present study describes the development of a novel multicomponent, cascade approach for indole synthesis. Various substituted indole derivatives were obtained from simple reagents, such as unfunctionalized alkenes, diazonium salts, and sodium triflinate, by using an established straightforward and regioselective method. The method is based on the radical trifluoromethylation of alkenes as an entry into Fischer indole synthesis. Besides indole synthesis, the application of the multicomponent cascade reaction to the synthesis of pyrazoles and pyridazinones is described.
Enantio‐ and Diastereoselective Access to Distant Stereocenters Embedded within Tetrahydroxanthenes: Utilizing ortho‐Quinone Methides as Reactive Intermediates in Asymmetric Brønsted Acid Catalysis
Authors: Hsiao Chien‐Chi , Liao Hsuan‐Hung , Rueping Magnus
Published: October 2014

A protocol for the highly enantioselective synthesis of 9‐substituted tetrahydroxanthenones by means of asymmetric Brønsted acid catalysis has been developed. A chiral binol‐based N‐triflyphosphoramide was found to promote the in situ generation of ortho‐quinone methides and their subsequent reaction with 1,3‐cyclohexanedione to provide the desired products with excellent enantioselectivities. In addition, a highly enantio‐ and diastereoselective Brønsted acid catalyzed desymmetrization of 5‐monosubstituted 1,3‐dicarbonyl substrates with ortho‐quinone methides gives rise to valuable tetrahydroxanthenes containing two distant stereocenters.
Chemoenzymatic Synthesis of Spinosyn A
Authors: Kim Hak Joong , Choi Sei‐hyun , Jeon Byung‐sun , Kim Namho , Pongdee Rongson , Wu Qingquan , Liu Hung‐wen
Published: October 2014

Following the biosynthesis of polyketide backbones by polyketide synthases (PKSs), post‐PKS modifications result in a significantly elevated level of structural complexity that renders the chemical synthesis of these natural products challenging. We report herein a total synthesis of the widely used polyketide insecticide spinosyn A by exploiting the prowess of both chemical and enzymatic methods. As more polyketide biosynthetic pathways are characterized, this chemoenzymatic approach is expected to become readily adaptable to streamlining the synthesis of other complex polyketides with more elaborate post‐PKS modifications.
Salt and pH sensitive semi‐interpenetrating polyelectrolyte hydrogels poly(HEMA‐co‐METAC)/PEG and its BSA adsorption behavior
Authors: Hu Yan‐Yan , Zhang Jing , Fang Qi‐Chen , Jiang Dong‐Mei , Lin Chu‐Cheng , Zeng Yi , Jiang Ji‐Sen
Published: October 2014

A novel semi‐interpenetrating poly(2‐hydroxyethyl methacrylate) (pHEMA) based polyelectrolyte hydrogel [p(HEMA‐co‐METAC)/PEG] was prepared by copolymerizing HEMA with the cationic monomer 2‐methacryloyloxyethyltrimethyl ammonium chloride (METAC) in the presence of polyethylene glycol (PEG) with different content and molecular weight (MW 4000 and 400). The chemical structure of the gels was confirmed by FT‐IR spectroscopy, morphology study was performed by scanning electron microscope (SEM), thermal stability was revealed by thermogravimetric analysis (TGA), and the mechanical properties were determined by electronic universal testing machine. Swelling studies showed introduction of cationic monomer METAC led to high water content, and the obvious salt and pH sensitive properties were observed which proved the smart behavior of the semi‐interpenetrating polymer networks (IPNs) gels. In addition, the effect of temperature and some important biological solution on swelling behavior were reported. Cytotoxicity test demonstrated that synthesized gels owned satisfactory cytocompatibility and were convenient for the application as biomaterials. Finally, the weak bovine serum albumin (BSA) adsorption on semi‐IPNs by introducing METAC and controlling the content of PEG in gels demonstrated that they were of good protein resistance effect in biomedical applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41537.
Autism Research Funding Allocation: Can Economics Tell Us If We Have Got It Right?
Authors: Zwicker Jennifer D. , Emery J.C. Herbert
Published: October 2014

There is a concern that the allocation of autism spectrum disorder (ASD) research funding may be misallocating resources, overemphasizing basic science at the expense of translational and clinical research. Anthony Bailey has proposed that an economic evaluation of autism research funding allocations could be beneficial for funding agencies by identifying under‐ or overfunded areas of research. In response to Bailey, we illustrate why economics cannot provide an objective, technical solution for identifying the “best” allocation of research resources. Economic evaluation has its greatest power as a late‐stage research tool for interventions with identified objectives, outcomes, and data. This is not the case for evaluating whether research areas are over‐ or underfunded. Without an understanding of how research funding influences the likelihood and value of a discovery, or without a statement of the societal objectives for ASD research and level of risk aversion, economic analysis cannot provide a useful normative evaluation of ASD research. Autism Res 2014, 7: 704–711. © 2014 International Society for Autism Research, Wiley Periodicals, Inc.
Anatomy of sex: Revision of the new anatomical terms used for the clitoris and the female orgasm by sexologists
Authors: Puppo Vincenzo , Puppo Giulia
Published: October 2014

Sexual medicine experts and sexologists must spread certainties on the biological basis of the female orgasm to all women, not hypotheses or personal opinions. Therefore, they must use scientific anatomical terminology. The anatomy of the clitoris and the female orgasm are described in textbooks, but some researchers have proposed a new anatomical terminology for the sexual response in women. The internal/inner clitoris does not exist: the entire clitoris is an external organ. The clitoris is not composed of two arcs but of the glans, body, and crura or roots. “Clitoral bulbs” is an incorrect term from an embryological and anatomical viewpoint: the correct term is “vestibular bulbs.” The bulbocavernosus muscles are implicated in inferior vaginismus, while the pubovaginal muscle is responsible for superior vaginismus. The clitoral or clitoris‐urethro‐vaginal complex has no embryological, anatomical and physiological support: the vagina has no anatomical relationship with the clitoris, and the clitoris is a perineal organ while the supposed G‐spot is in the pelvic urethra. G‐spot/vaginal/clitoral orgasm, vaginally activated orgasm, and clitorally activated orgasm, are incorrect terms: like “male orgasm,” “female orgasm” is the correct term. The “vaginal” orgasm that some women report is always caused by the surrounding erectile organs (triggers of female orgasm). The male penis cannot come in contact with the venous plexus of Kobelt or with the clitoris during vaginal intercourse. Also, female ejaculation, premature ejaculation, persistent genital arousal disorder (PGAD), periurethral glans, vaginal–cervical genitosensory component of the vagus nerve, and G‐spot amplification, are terms without scientific basis. Female sexual satisfaction is based on orgasm and resolution: in all women, orgasm is always possible if the female erectile organs, i.e. the female penis, are effectively stimulated during masturbation, cunnilingus, partner masturbation, or during vaginal/anal intercourse if the clitoris is simply stimulated with a finger. Clin. Anat. 28:293–304, 2015. © 2014 Wiley Periodicals, Inc.
The Claisen Rearrangement – Part 1: Mechanisms and Transition States, Revisited with Quantum Mechanical Calculations and Ultrashort Pulse Spectroscopy
Authors: Zelentsov Sergei , Hessel Volker , Shahbazali Elnaz , Noël Timothy
Published: October 2014

The Claisen rearrangement is an ideal candidate for mechanistic and transition‐state analysis. Recently, physical‐chemistry investigations, in particular relying on quantum mechanics and modern fs‐pulse (‘short‐time') laser spectroscopy, have given totally new insights here. At the same time, flow chemistry has emerged, offering considerable processing advances over batch processing. It is also known to be much powerful with inline flow sensing techniques. Yet, both key innovations have not been bridged so far and thus there is an eminent knowledge gap in mechanistic analysis of reactions. This two‐review compilation is a first step to close this gap. Part 1 focuses on the insight which quantum‐mechanical calculations can add to the existing knowledge based on heuristic, handy interpretation of reaction experiments in the light of electrodensity distributions. Quantum‐mechanical calculation can provide geometric key data and short‐time laser spectroscopy can verify this and deepen it in the sense of a comprehensive vibration analysis. In this way, prior structural assumptions can be confirmed or turned to be falsified and there is potential to resolve the uncertainty.
Subdural hemorrhage – a serious complication post‐intrathecal chemotherapy. A case report and review of literature
Authors: Chia Xiu Xian , Bazargan Ali
Published: October 2014

Key Clinical Message

We need to have a high index of suspicion for subdural hemorrhage (SDH) post‐lumbar puncture in hematological patients given their increased risk and the significant morbidity and mortality associated with SDHs.
New Cofactor‐Independent Hydration Biocatalysts: Structural, Biochemical, and Biocatalytic Characteristics of Carotenoid and Oleate Hydratases
Authors: Hiseni Aida , Arends Isabel W. C. E. , Otten Linda G.
Published: October 2014

In industrial biocatalytic processes the class of lyases (EC 4) is underrepresented and only a few enzymes are used in industrial scale reactions. Hydro‐lyases (EC 4.2.1) catalyze the non‐hydrolytic and non‐oxidative addition of water to a CC bond. Without a biocatalyst, this reaction proceeds under strong acidic conditions with no enantioselectivity. From a chemical point of view carotenoid 1,2‐hydratase (CrtC) performs a very challenging addition of water to an isolated CC bond. This hydration reaction proceeds without assistance of electron withdrawing groups or transition metals, which makes it very interesting from both an industrial, as well as enzymatic point of view. Oleate hydratase (OHase) catalyzes the enantioselective conversion of oleic acid into 10‐hydroxystearic acid. The crystal structure of OHase from Lactobacillus acidophilus was published recently, which contributes to the understanding of this enzyme. These enzymes could broaden the organic chemist’s toolbox.
Microkinetic Modeling of the Fischer–Tropsch Synthesis over Cobalt Catalysts
Authors: Azadi Pooya , Brownbridge George , Kemp Immanuel , Mosbach Sebastian , Dennis John S. , Kraft Markus
Published: October 2014

We present a detailed microkinetic analysis of the Fischer–Tropsch synthesis on a Co/γ‐Al2O3 catalyst over the full range of syngas conversions. The experiments were performed in a Carberry spinning basket batch reactor at initial H2/CO ratios between 1.8 and 2.9, temperatures of 469 and 484 K, and initial pressures of 2 MPa. A reaction mechanism based on the H2‐assisted CO activation pathway, which comprises 128 elementary reactions with 85 free parameters, was proposed to explain the experimental results. Each of these elementary reactions belongs to one of the following reaction groups: adsorption–desorption, monomer formation, chain growth, hydrogenation–hydrogen abstraction, or water–gas shift. A two‐stage parameter estimation method, based on a quasi‐random global search followed by a gradient‐free local optimization, has been used to calculate the values of pre‐exponential factors and activation energies. The use of data obtained from batch experiments enabled an effective analysis of dominating reactions at different stages of syngas conversions.
Activity and Stability of Lipase Preparations from Penicillium corylophilum: Potential Use in Biocatalysis
Authors: Romero Cintia M. , Baigorí Mario D. , Baron Alessandra Machado , Krieger Nadia , Pera Licia M.
Published: October 2014

Biocatalysts with lipase activity were produced by Penicillium corylophilum under basal and olive oil‐induced conditions. In the presence of olive oil, both the extracellular and the mycelium‐bound lipase activities were increased significantly. The four biocatalysts maintained a residual lipase activity after incubation in a wide pH range showing high stability in a defined acidic to neutral pH range. Some differences between biocatalyst residual activities were also observed after incubation at various temperatures or in the presence of organic solvents such as methanol, ethanol, acetone, butanol, hexanol, n‐hexane, and heptane. Enzymes which are stable in the presence of ethanol or butanol could be useful in ecofriendly processes for biodiesel production.
Electronic Circular Dichroism of Chiral Alkenes: B3LYP and CAM‐B3LYP Calculations
Authors: Jorge Francisco E. , Jorge Sara S. , Suave Rogério N.
Published: October 2014

Time‐dependent density functional theory (TDDFT) calculations of electronic circular dichroism (ECD) are widely used to determine absolute configurations (ACs) of chiral molecules. Two very popular DFT exchange‐correlation functionals, one hybrid (B3LYP) and one long‐range corrected (CAM‐B3LYP), along with a hierarchical sequence of basis sets were investigated, and the ECD spectra predicted for eight alkenes and compared to gas‐phase experimental spectra. Little variation in predicted ECD spectra was found with the basis set size enlargement, but the sensitivity to the functional is greater. Good agreement was obtained only with the CAM‐B3LYP functional, leading to the conclusion that TDDFT calculations of ECD spectra can routinely provide reliable ACs if and only if an appropriate functional is used. For camphene, twistene, syn‐(E)‐bisfenchylidene, and phyllocladene, solvent effects were estimated. Chirality 27:23–31, 2015. © 2014 Wiley Periodicals, Inc.
Synthesis of Novel Camphor‐Derived Bifunctional Thiourea Organocatalysts
Authors: Ričko Sebastijan , Golobič Amalija , Svete Jurij , Stanovnik Branko , Grošelj Uroš
Published: October 2014

Synthesis and catalyst performance of 2,3‐ (types B and C) and 2,8‐disubstituted (type D) thiourea bifunctional organocatalysts was attempted. The synthesis of catalyst of type B has, so far, not been realized, while catalysts of type C, i.e., the 2,3‐exo‐ and the 2‐endo‐3‐exo‐thiourea catalysts, were prepared in six steps starting from (+)‐camphor. The catalysts of type D were prepared from (+)‐camphor in eight steps. All the potential catalysts as well as most of the intermediate products were carefully structurally characterized. The thiourea bifunctional organocatalysts were tested in a model reaction of Michael addition of dimethyl malonate to trans‐β‐nitrostyrene. Chirality 27:39–52, 2015. © 2014 Wiley Periodicals, Inc.
Bioreducible Guanidinylated Polyethylenimine for Efficient Gene Delivery
Authors: Lee Duhwan , Lee Yeong Mi , Jeong Cherlhyun , Lee Jun , Kim Won Jong
Published: October 2014

Cationic polymers are known to afford efficient gene transfection. However, cytotoxicity remains a problem at the molecular weight for optimal DNA delivery. As such, optimized polymeric gene delivery systems are still a sought‐after research goal. A guanidinylated bioreducible branched polyethylenimine (GBPEI‐SS) was synthesized by using a disulfide bond to crosslink the guanidinylated BPEI (GBPEI). GBPEI‐SS showed sufficient plasmid DNA (pDNA) condensation ability. The physicochemical properties of GBPEI‐SS demonstrate that it has the appropriate size (∼200 nm) and surface potential (∼30 mV) at a nitrogen‐to‐phosphorus ratio of 10. No significant toxicity was observed, possibly due to bioreducibility and to the guanidine group delocalizing the positive charge of the primary amine in BPEI. Compared with the nonguanidinylated analogue, BPEI‐SS, GBPEI‐SS showed enhanced transfection efficiency owing to increased cellular uptake and efficient pDNA release by cleavage of disulfide bonds. This system is very efficient for delivering pDNA into cells, thereby achieving high transfection efficiency and low cytotoxicity.
The Brownian Fan
Authors: Hairer Martin , Weare Jonathan
Published: October 2014

We provide a mathematical study of the modified diffusion Monte Carlo (DMC) algorithm introduced in the companion article [3]. DMC is a simulation technique that uses branching particle systems to represent expectations associated with Feynman‐Kac formulae. We provide a detailed heuristic explanation of why, in cases in which a stochastic integral appears in the Feynman‐Kac formula (e.g., in rare event simulation, continuous time filtering, and other settings), the new algorithm is expected to converge in a suitable sense to a limiting process as the time interval between branching steps goes to 0. The situation studied here stands in stark contrast to the “naï ve” generalization of the DMC algorithm, which would lead to an exponential explosion of the number of particles, thus precluding the existence of any finite limiting object. Convergence is shown rigorously in the simplest possible situation of a random walk, biased by a linear potential. The resulting limiting object, which we call the “Brownian fan,” is a very natural new mathematical object of independent interest. © 2014 Wiley Periodicals, Inc.
An anonymous and untraceable password‐based authentication scheme for session initiation protocol using smart cards
Authors: Farash Mohammad Sabzinejad , Attari Mahmoud Ahmadian
Published: October 2014

Recently, Zhang et al. proposed a password‐based authenticated key agreement for session initiation protocol (Int J Commun Syst 2013, doi:10.1002/dac.2499). They claimed that their protocol is secure against known security attacks. However, in this paper, we indicate that the protocol by Zhang et al. is vulnerable to impersonation attack whereby an active adversary without knowing the user's password is able to introduce himself/herself as the user. In addition, we show that the protocol by Zhang et al. suffers from password changing attack. To overcome the weaknesses, we propose an improved authentication scheme for session initiation protocol. The rigorous analysis shows that our scheme achieves more security than the scheme by Zhang et al. Copyright © 2014 John Wiley & Sons, Ltd.
Validation of and comparison between a semidistributed rainfall–runoff hydrological model (PREVAH) and a spatially distributed snow‐evolution model (SnowModel) for snow cover prediction in mountain ecosystems
Authors: Randin Christophe F. , Dedieu Jean‐Pierre , Zappa Massimiliano , Long Li , Dullinger Stefan
Published: October 2014

Snow cover is an important control in mountain environments and a shift of the snow‐free period triggered by climate warming can strongly impact ecosystem dynamics. Changing snow patterns can have severe effects on alpine plant distribution and diversity. It thus becomes urgent to provide spatially explicit assessments of snow cover changes that can be incorporated into correlative or empirical species distribution models (SDMs).

Here, we provide for the first time a with a lower overestimation comparison of two physically based snow distribution models (PREVAH and SnowModel) to produce snow cover maps (SCMs) at a fine spatial resolution in a mountain landscape in Austria. SCMs have been evaluated with SPOT‐HRVIR images and predictions of snow water equivalent from the two models with ground measurements. Finally, SCMs of the two models have been compared under a climate warming scenario for the end of the century.

The predictive performances of PREVAH and SnowModel were similar when validated with the SPOT images. However, the tendency to overestimate snow cover was slightly lower with SnowModel during the accumulation period, whereas it was lower with PREVAH during the melting period. The rate of true positives during the melting period was two times higher on average with SnowModel with a lower overestimation of snow water equivalent.

Our results allow for recommending the use of SnowModel in SDMs because it better captures persisting snow patches at the end of the snow season, which is important when modelling the response of species to long‐lasting snow cover and evaluating whether they might survive under climate change. Copyright © 2014 John Wiley & Sons, Ltd.
Complexation of NpV Ions with 1,10‐Phenanthroline‐2,9‐dicarboxylic Acid: Spectrophotometric and Microcalorimetric Studies
Authors: Yang Yanqiu , Zhang Zhicheng , Luo Shunzhong , Rao Linfeng
Published: October 2014

The complexation of NpV ions with a tetradentate ligand with oxygen and nitrogen donors, 1,10‐phenanthroline‐2,9‐dicarboxylic acid (denoted as H2L), was studied in aqueous solutions by spectrophotometric and calorimetric methods. NpV ions form a very strong 1:1 complex, NpO2L–, with the stability constant log β = 11.73 ± 0.02 in 0.1 M NaClO4 at 25 °C. It is a much stronger complex than those of NpV ions with related ligands such as picolinic acid or dipicolinic acid, as the higher denticity of 1,10‐phenanthroline‐2,9‐dicarboxylic acid results in a larger entropic effect on the complexation. It is expected that the amide derivatives of 1,10‐phenanthroline‐2,9‐dicarboxylic acid would be excellent extractants in the separation of NpV ions, which are problematic in actinide separation processes owing to their very low extractability by many extractants.
Polyrotaxaned versus Interdigitated Super‐Arrays of Loop‐and‐Chain Strands: Role of the Anion in Formation of Silver(0) Particles
Authors: Jang Jaeseong , Noh Tae Hwan , Park Jin Kyoon , Shim Yoon‐Bo , Jung Ok‐Sang
Published: October 2014

Self‐assembly of AgX (X– = BF4–, ClO4–, and NO3–) with C3‐symmetric 1,3,5‐tris(isonicotinoyloxyethyl)cyanurate (L) yields 1D loop‐and‐chain strands. However, the formation of a super‐array of strands depends on the nature of the polyatomic anions: BF4– and ClO4– anions induce 1D polyrotaxaned loop‐and‐chain strands, whereas NO3– anion leads to the formation of 2D‐like interdigitated loop‐and‐chain strands in the crystalline state. Calcination of [Ag3(L)2]3X (X– = BF4– and NO3–) crystals at 500 °C produces silver(0) particles, whereas the same treatment of [Ag3(L)2]3ClO4 crystals affords a mixture of silver(0) and silver(I) chloride. The rates of formation of Ag0 nanoparticles by reduction of crystalline products using ascorbic acid are in the order X– = ClO4– > BF4– > NO3–, and their crystalline morphologies are dependent on the nature of the polyatomic anions.
Oxone®/KI‐Mediated Nitration of Alkenes and Alkynes: Synthesis of Nitro‐ and β‐Iodonitro‐Substituted Alkenes
Authors: Hlekhlai Sornsiri , Samakkanad Natthapol , Sawangphon Tassaporn , Pohmakotr Manat , Reutrakul Vichai , Soorukram Darunee , Jaipetch Thaworn , Kuhakarn Chutima
Published: October 2014

Oxone® (2KHSO5·KHSO4·K2SO4) was used to promote the nitration of alkenes and alkynes with sodium nitrite (NaNO2) and potassium iodide (KI). This stable, easy‐to‐handle, and environmentally benign oxidant was used under mild conditions (room temperature) and provided short reaction times. Styrene derivatives that did not contain electron‐donating groups afforded the corresponding nitro alkenes in moderate to good yields, whereas aliphatic alkenes and electron‐deficient alkenes were not good substrates. Under similar reaction conditions, aryl alkynes yielded β‐iodonitro alkenes.
Neocryptolepine (Cryprotackieine), A Unique Bioactive Natural Product: Isolation, Synthesis, and Profile of Its Biological Activity
Authors: Bracca Andrea B. J. , Heredia Daniel A. , Larghi Enrique L. , Kaufman Teodoro S.
Published: October 2014

The widely varying different approaches to the total synthesis of the indoloquinoline alkaloid neocryptolepine are discussed. Aspects relating to the isolation of the natural product from Cryptolepis sanguinolenta, as well as its performance in various biological tests and spectroscopic studies involving the natural product, are also reviewed.
Phase‐Transfer‐Catalyst‐Mediated Domino Reaction of γ‐Nitro Ketones with Chalcones: Approach to Functionalized Six‐Membered‐Ring Carbocycles
Authors: Yu Lu , Yang Qingjing , Li Pengfei
Published: October 2014

Domino reactions between γ‐nitro ketones and chalcones for the construction of functionalized six‐membered‐ring carbocycles using a phase‐transfer catalyst have been developed. In the presence of tetrabutylammonium iodide and potassium hydroxide, domino reactions between γ‐nitro ketones and a series of chalcones proceeded smoothly to give the cyclic products in moderate to high yields with high diastereoselectivities. Importantly, multiply substituted and functionalized six‐membered‐ring carbocycles could be efficiently prepared in one pot using this domino strategy.
Reactions of p‐Quinols with Aldehydes and Imines: Stereoselective Access to Polyheterobicyclic and Tricyclic Systems
Authors: García‐García Carolina , Redondo María C. , Ribagorda María , Carreño M. Carmen
Published: October 2014

Dihydrobenzo[1,3]dioxolanones, tetrahydrobenzo[d]oxazolones and heterotricyclic derivatives have been stereoselectively synthesized from p‐quinols upon reaction with aldehydes or benzaldimines under basic catalysis. Reactions occurred in an experimentally simple one‐pot procedure through a domino sequence of two or three reactions. The choice of 4‐(dimethylamino)pyridine (DMAP) or 1,4‐diazabicyclo[2.2.2]octane (DABCO) as catalyst and MeOH, tetrahydrofuran (THF), or dichloromethane as solvent was essential to achieve the synthesis of bicyclic dioxolanes from aldehydes or bicyclic or tricyclic N,O‐aminals from imines. The stereochemical course of these processes is highly dependent on the nature of the electrophiles.
Synthesis of a Photostable Energy‐Transfer Pair for “DNA Traffic Lights”
Authors: Bohländer Peggy R. , Wagenknecht Hans‐Achim
Published: October 2014

A new cyano‐substituted thiazole red derivative as a red emitter and a novel green fluorescent donor dye of the cyanine styryl type were synthesized in good yields. Characterization of their optical properties revealed excellent photostabilities and large apparent Stokes' shifts. Both dyes can be incorporated into oligonucleotides through postsynthetic “click”‐type chemistry and combined in a diagonal arrangement in double‐stranded DNA. As a result, both dyes combine to an energy‐transfer pair in DNA that shows remarkable optical properties such as significant emission wavelength shift from green to red upon hybridization owing to high energy‐transfer efficiency between the two dyes and remarkable emission red/green color contrast ratio. The combination of these dyes as an energy‐transfer pair according to our concept of “DNA traffic lights” has high potential for applications in molecular imaging.
Im Zwischendrin mit Kanzlerin
Authors: Finetti Marco
Published: October 2014

Durchaus nicht betrübt, aber auch nicht völlig ungetrübt: In Frankfurt genoss die DFG den Augenblick des Miteinanders – die wissenschaftspolitische Gemengelage dabei stets im Blick.
Wie lange noch?
Authors: Ahrens Mark Alexander , Sanio David
Published: October 2014

Unablässiger Verkehr, Korrosion und Witterung setzen dem Spannstahl in Brücken mächtig zu. Bauingenieure setzen auf Rechenmodelle, mit denen sich der Ermüdungsfortschritt und damit die Nutzungsdauer der Bauwerke besser einschätzen lässt. Wie sicher die Prognosen sind, ist von der Güte der Daten und der Genauigkeit der angewandten Verfahren ab.
Der Künstler spricht mit sich selbst
Authors: Arnhold Hermann , Pirsig‐Marshall Tanja
Published: October 2014

Als Maler gehört August Macke zu den Ikonen des Expressionismus. Weit weniger bekannt ist sein zeichnerisches Werk – dabei gehört es zu den eindrucksvollsten künstlerischen Leistungen des 20. Jahrhunderts. Ein Digitalisierungsprojekt in Münster macht dieses facettenreiche Œuvre jetzt online zugänglich.
Dying and multiplying life
Authors: Rodríguez‐Arias David
Published: October 2014

It was only after James P. Lovette's death, in 2006, that I discovered that the twenty‐four‐year‐old colleague and friend with whom I had spent so many afternoons debating issues in organ transplantation had been the first successful child heart transplantee in the world and one of the longest‐living survivors of a second transplant. During the years we met, he never even hinted at the fact that three different hearts had beaten in his chest. The revelation that his life had been an almost uninterrupted chain of medical challenges suddenly made me appreciate his quirkiness in a whole new light.

Organ transplantation crudely exemplifies a traditional moral dilemma between means and ends: in order to save a life, someone else has to die. Bioethicists involved in this field have the role of identifying the ethical issues surrounding organ donation and helping others to argue in an intelligible and convincing way. In my view, bioethicists have the obligation to foster a discussion as open and transparent as possible on these matters. Still, I sometimes fear that I may be helping to cause unnecessary harms to potential recipients who are desperately waiting for a vital organ. Scholars would be chillingly cold if their quest for truth systematically came at the cost of lives lost. Every life can be meaningful and provide meaning to many others. This is true even with organ recipients, who often have short lives full of considerable suffering.
Learning about Teaching
Authors: Kaebnick Gregory E.
Published: October 2014

There are three broad themes in this issue of the Hastings Center Report. First, a special report published as a supplement to the issue addresses the medical and health policy issues faced by lesbian, gay, bisexual, and transgender patients. Inside the issue, the two articles take up questions about how caregivers may justify a refusal to provide a medical service that a patient has requested. The issue also contains a set of essays that have emerged from a collaborative effort by The Hastings Center and the Presidential Commission for the Study of Bioethical Issues to promote scholarly engagement with the practical problem of teaching caregivers, researchers, scientists, and others to address bioethical problems. What appears here is the first installment of a series that will appear in the pages of the Report well into the 2015 volume.