bluuebunny/crossref_metadata_2025 huggingface dataset:
Aortic aneurysm and craniosynostosis in a family with Cantu syndrome
Authors: Hiraki Yoko , Miyatake Satoko , Hayashidani Michiko , Nishimura Yutaka , Matsuura Hiroo , Kamada Masahiro , Kawagoe Takuji , Yunoki Keiji , Okamoto Nobuhiko , Yofune Hiroko , Nakashima Mitsuko , Tsurusaki Yoshinori , Satisu Hirotomo , Murakami Akira , Miyake Noriko , Nishimura Gen , Matsumoto Naomichi
Published: November 2013

Cantu syndrome is an autosomal dominant overgrowth syndrome associated with facial dysmorphism, congenital hypertrichosis, and cardiomegaly. Some affected individuals show bone undermodeling of variable severity. Recent investigations revealed that the disorder is caused by a mutation in ABCC9, encoding a regulatory SUR2 subunit of an ATP‐sensitive potassium channel mainly expressed in cardiac and skeletal muscle as well as vascular smooth muscle. We report here on a Japanese family with this syndrome. An affected boy and his father had a novel missense mutation in ABCC9. Each patient had a coarse face and hypertrichosis. However, cardiomegaly was seen only in the boy, and macrosomia only in the father. Skeletal changes were not evident in either patient. Craniosynostosis in the boy and the development of aortic aneurysm in the father are previously undescribed associations with Cantu syndrome. © 2013 Wiley Periodicals, Inc.
Familial microduplication of 17q23.1–q23.2 involving TBX4 is associated with congenital clubfoot and reduced penetrance in females
Authors: Peterson Jess F. , Ghaloul‐Gonzalez Lina , Madan‐Khetarpal Suneeta , Hartman Jessica , Surti Urvashi , Rajkovic Aleksandar , Yatsenko Svetlana A.
Published: November 2013

Congenital clubfoot is a heterogeneous disorder that can result in functional disability, deformity, and pain if left untreated. Although the etiology is considered multifactorial in the majority of cases, a 17q23.1–q23.2 duplication has been reported in families with congenital clubfoot characterized by variable expressivity and incomplete penetrance. The candidate gene within the duplicated region is TBX4, a T‐box transcription factor required for normal hind limb development. We describe a familial 2.15 Mb duplication in the 17q23.1–q23.2 region identified in a mother, daughter, and two sons. The male proband was referred for genetic evaluation due to multiple congenital anomalies including bilateral clubfoot, dysplastic hips, multiple heart defects, microcephaly, midfacial hypoplasia, brain anomalies on MRI scan, seizure disorder, optic nerve hypoplasia, hearing loss, and bilateral vocal cord paralysis. Cytogenetic testing on family members identified the 17q23.1–q23.2 duplication in both older siblings and the mother. In this family both male siblings had clubfoot, while females were phenotypically normal. Although TBX4 remains the candidate gene for congenital clubfoot involving 17q23.1–q23.2 duplications, the explanation for variable expressivity and penetrance remains unknown. © 2013 Wiley Periodicals, Inc.
An empirical comparison of short tandem repeats (STRs) and single nucleotide polymorphisms (SNPs) for relatedness estimation in Chinese rhesus macaques (Macaca mulatta)
Authors: Ross Cody T. , Weise Jessica A. , Bonnar Sarah , Nolin David , Satkoski Trask Jessica , Smith David Glenn , Ferguson Betsy , Ha James , Kubisch H. Michael , Vinson Amanda , Kanthaswamy Sree
Published: November 2013

We compare the effectiveness of short tandem repeat (STR) and single nucleotide polymorphism (SNP) genotypes for estimating pairwise relatedness, using molecular data and pedigree records from a captive Chinese rhesus macaque population at the California National Primate Research Center. We find that a panel of 81 SNPs is as effective at estimating first‐order kin relationships as a panel of 14 highly polymorphic STRs. We note, however, that the selected STRs provide more precise predictions of relatedness than the selected SNPs, and may be preferred in contexts that require the discrimination of kin related more distantly than first‐order relatives. Additionally, we compare the performance of three commonly used relatedness estimation algorithms, and find that the Wang [2002] algorithm outperforms other algorithms when analyzing STR data, while the Queller & Goodnight [1989] algorithm outperforms other algorithms when analyzing SNP data. Future research is needed to address the number of SNPs required to reach the discriminatory power of a standard STR panel in relatedness estimation for primate colony management. Am. J. Primatol. 76:313–324, 2014. © 2013 Wiley Periodicals, Inc.
NLRP3 inflammasome contributes to inflammation after intracerebral hemorrhage
Authors: Ma Qingyi , Chen Sheng , Hu Qin , Feng Hua , Zhang John H. , Tang Jiping
Published: November 2013

Objective

The NLRP3 (NALP3, cryopyrin) inflammasome, a key component of the innate immune system, facilitates caspase‐1 and interleukin (IL)−1β processing, which amplifies the inflammatory response. Here, we investigated whether NLRP3 knockdown decreases neutrophil infiltration, reduces brain edema, and improves neurological function in an intracerebral hemorrhage (ICH) mouse model. We also determined whether mitochondrial reactive oxygen species (ROS) governed by mitochondrial permeability transition pores (mPTPs) would trigger NLRP3 inflammasome activation following ICH.

Methods

ICH was induced by injecting autologous arterial blood (30μl) into a mouse brain. NLRP3 small interfering RNAs were administered 24 hours before ICH. A mPTP inhibitor (TRO‐19622) or a specific mitochondria ROS scavenger (Mito‐TEMPO) was coinjected with the blood. In naive animals, rotenone, which is a respiration chain complex I inhibitor, was applied to induce mitochondrial ROS production, and followed by TRO‐19622 or Mito‐TEMPO treatment. Neurological deficits, brain edema, enzyme‐linked immunosorbent assay, Western blot, in vivo chemical cross‐linking, ROS assay, and immunofluorescence were evaluated.

Results

ICH activated the NLRP3 inflammasome. NLRP3 knockdown reduced brain edema and decreased myeloperoxidase (MPO) levels at 24 hours, and improved neurological functions from 24 to 72 hours following ICH. TRO‐19622 or Mito‐TEMPO reduced ROS, NLRP3 inflammasome components, and MPO levels following ICH. In naive animals, rotenone administration induced mPTP formation, ROS generation, and NLRP3 inflammasome activation, which were then reduced by TRO‐19622 or Mito‐TEMPO.

Interpretation

The NLRP3 inflammasome amplified the inflammatory response by releasing IL‐1β and promoting neutrophil infiltration following ICH. Mitochondria ROS may be a major trigger of NLRP3 inflammasome activation. The results of our study suggest that the inhibition of the NLRP3 inflammasome may effectively reduce the inflammatory response following ICH.ANN NEUROL 2014;75:209–219
Organische Elektronendonoren als leistungsfähige Ein‐Elektronen‐Reduktionsmittel in der organischen Synthese
Authors: Broggi Julie , Terme Thierry , Vanelle Patrice
Published: November 2013

In der organischen Chemie wird die Ein‐Elektronen‐Reduktion häufig verwendet, um eine Radikalbildung durch den schrittweisen Transfer von einem oder zwei Elektronen von einem Donor auf ein organisches Substrat zu realisieren. Neben den metallischen Reagentien haben sich Reduktionsmittel auf der Basis neutraler organischer Moleküle, die einen Ein‐Elektronen‐Transfer ermöglichen, als eine attraktive neue Quelle für reduzierende Elektronen erwiesen. In den letzten zwanzig Jahren ist eine besondere Klasse organischer Reduktionsmittel, die elektronenreichen Olefine, zunehmend in Erscheinung getreten, und ihre Anwendung in der organischen Synthese hat sich vervielfacht. In diesem Aufsatz werden die verschiedenen Arten von organischen Donoren und ihre spezifischen Besonderheiten in organischen Umwandlungen zusammengefasst und diskutiert.
Zur Metallierung von Benzol und Toluol durch die Schlosser‐Base: ein superbasischer Li2K4‐Cluster unter Beteiligung von PhK, PhLi und tBuOLi
Authors: Unkelbach Christian , O'Shea Donal F. , Strohmann Carsten
Published: November 2013

Die Metallierung von Benzol durch die Schlosser‐Base (nBuLi/tBuOK) läuft in THF glatt bei niedrigen Temperaturen unter Bildung eines diskreten, gemischtmetallischen Li2K4‐Clusters ab, der neben tert‐Butoxid auch Phenylanionen enthält (siehe Bild). Das Aggregat selbst weist mit der Metallierung von Toluol superbasische Reaktivität auf. Das auf diesem Weg erhaltene Benzylanion zeigt π‐Wechselwirkungen zum Kaliumgegenion, unter Bildung eines 2D‐Koordinationspolymers.
Diaryl Sulfoxides from Aryl Benzyl Sulfoxides: A Single Palladium‐Catalyzed Triple Relay Process
Authors: Jia Tiezheng , Bellomo Ana , Montel Sonia , Zhang Mengnan , EL Baina Kawtar , Zheng Bing , Walsh Patrick J.
Published: November 2013

A novel approach to produce diaryl sulfoxides from aryl benzyl sulfoxides is reported. Optimization of the reaction conditions was performed using high‐throughput experimentation techniques. The [Pd(dba)2]/NiXantPhos catalyst system successfully promotes a triple relay process involving sulfoxide α‐arylation, CS bond cleavage, and CS bond formation. The byproduct benzophenone is formed by an additional palladium‐catalyzed process. It is noteworthy that palladium‐catalyzed benzylative CS bond cleavage of sulfoxides is unprecedented. A wide range of aryl benzyl sulfoxides, as well as alkyl benzyl sulfoxides with various (hetero)aryl bromides were employed in the triple relay process in good to excellent yields (85–99 %). Moreover, aryl methyl sulfoxides, dibenzyl sulfoxides, and dimethylsulfoxide could be utilized to generate diaryl sulfoxides involving multiple catalytic cycles by a single catalyst.
Catalytic Enantioselective Oxidative Cross‐Coupling of Benzylic Ethers with Aldehydes
Authors: Meng Zhilin , Sun Shutao , Yuan Huiqing , Lou Hongxiang , Liu Lei
Published: November 2013

The first one‐pot enantioselective oxidative coupling of cyclic benzylic ethers with aldehydes has been developed. A variety of benzylic ethers were transformed into the corresponding oxygen heterocycles with high enantioselectivity. Mechanistic experiments were conducted to determine the nature of the reaction intermediates. The application of this strategy to coupling reactions with other nucleophiles besides aldehydes was also explored.
Organic Electron Donors as Powerful Single‐Electron Reducing Agents in Organic Synthesis
Authors: Broggi Julie , Terme Thierry , Vanelle Patrice
Published: November 2013

One‐electron reduction is commonly used in organic chemistry for the formation of radicals by the stepwise transfer of one or two electrons from a donor to an organic substrate. Besides metallic reagents, single‐electron reducers based on neutral organic molecules have emerged as an attractive novel source of reducing electrons. The past 20 years have seen the blossoming of a particular class of organic reducing agents, the electron‐rich olefins, and their application in organic synthesis. This Review gives an overview of the different types of organic donors and their specific characteristics in organic transformations.
Synthesis, film morphology, and performance on cotton substrates of dodecyl/piperazine functional polysiloxane
Authors: Min Caina , Pu Qun , Yang Liu , Fan Hong
Published: November 2013

A novel polysiloxane bearing dodecyl and epoxy side groups (DESO) was synthesized as an intermediate through hydrosilylation of polymethylhydrosiloxane with allyl glycidyl ether and 1‐dodecene. Then, dodecyl/piperazine functional polysiloxane (DPSO) was prepared through the reaction of N‐aminoethylpiperazine with DESO. The chemical structure of DPSO was characterized with FTIR and 1H‐NMR spectroscopy and its application performance on cotton fabrics was studied. DPSO with dodecyl side groups gifted the treated fabrics with good wettability and whiteness compared with piperazine functional polysiloxane, while with a slightly reduced softness as well as thickening handle. Film morphology, orientation, and performance on cotton substrates of DPSO were investigated by scanning electron microscope, atomic force microscopy, X‐ray photoelectron microscope, and so on. Affected by the dodecyl side groups, DPSO formed relatively hydrophilic, macroscopically smooth but actually uneven films with many dodecyl side chain pillars on the treated substrate surfaces. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40186.
Synthesis of 1,2,3‐Triazolyl Nucleoside Analogs as Potential Anti‐Influenza A (H3N2 Subtype) Virus Agents
Authors: Elayadi Hanane , Smietana Michael , Vasseur Jean J. , Balzarini Jan , Lazrek Hassan B.
Published: November 2013

Montmorillonite K10 impregnated with copper dichloride and potassium iodide (CuCl2/KI/K10) was used as catalyst in the cycloaddition of azides and propargylnucleobases, to provide the corresponding 1,4‐disubstituted 1,2,3‐triazoles in good yield. All compounds 16–23 were evaluated for their antiviral activity in vitro. Compound 18 showed moderate inhibition against influenza virus A (H3N2).
The impact of volcanic eruptions in the period 2000–2013 on global mean temperature trends evaluated in the HadGEM2‐ES climate model
Authors: Haywood Jim M. , Jones Andy , Jones Gareth S.
Published: November 2013

The slow‐down in global warming over the last decade has lead to significant debate about whether the causes are of natural or anthropogenic origin. Using an ensemble of HadGEM2‐ES coupled climate model simulations we investigate the impact of overlooked modest volcanic eruptions. We deduce a global mean cooling of around −0.02 to −0.03 K over the period 2008–2012. Thus while these eruptions do cause a cooling of the Earth and may therefore contribute to the slow‐down in global warming, they do not appear to be the sole or primary cause.
Regional response of annual‐mean tropical rainfall to global warming
Authors: Huang Ping
Published: November 2013

Regional response of annual‐mean tropical rainfall to global warming is investigated based on 18 models from the Coupled Model Intercomparison Project 5. With surface warming, the climatological ascending circulation pumps up increased surface moisture and leads to a rainfall increase over the convergence zone, while the change in ascending flow induces a rainfall increase over the region with sea surface temperature (SST) increase exceeding the tropical mean, with a concomitant modification of background surface moisture and SST. These two effects form a hook‐like pattern of rainfall change over the tropical Pacific and an elliptic pattern over the northern Indian Ocean.
THE RELATIVE INFLUENCE OF MOTIVATING OPERATIONS FOR POSITIVE AND NEGATIVE REINFORCEMENT ON PROBLEM BEHAVIOR DURING DEMANDS
Authors: Call Nathan A. , Lomas Mevers Joanna E.
Published: November 2013

Research has demonstrated the feasibility of using positive reinforcement to treat problem behavior maintained by negative reinforcement. This line of research was extended in the current study. A functional analysis (FA) was conducted that suggested problem behavior was maintained by positive and negative reinforcement. Following the FA, a demand analysis was conducted with three demand conditions: one that replicated the demand condition from the FA, one that included presession exposure to a preferred item, and another that included presession exposure to preferred items and access to those items during breaks from demands. Although problem behavior occurred in all three demand conditions, within session analyses showed that problem behavior ceased during breaks from demands only when they included access to preferred items. This finding suggests that the motivating operation responsible for evoking problem behavior did not decrease when only a break was provided. Subsequent functional communication training and treatment analysis showed that treatments based on positive reinforcement were effective at reducing problem behavior, but those based on a negative reinforcement hypothesis were not. Copyright © 2013 John Wiley & Sons, Ltd.
Does the “C3 effect” offset the Δ2 effect, as regards the solution flexibility of aldoses?
Authors: Morris Mallory J. , Striegel André M.
Published: November 2013

The solution flexibility of carbohydrates influences a variety of molecular recognition and regulatory processes. For aldoses and other monosaccharides, this flexibility is dictated by the orientations of the various hydroxyl (OH) groups present, which influences conformer and anomer ratios, interactions among these OH groups, and interactions between them and the surrounding solvent. Depending on the number and position of axial OH groups, a variety of structures can coexist in solutions at equilibrium. In 1950, as part of his pioneering studies on the shape of pyranoside rings, Reeves described the Δ2 effect, the greater destabilization of the pyranose ring conformation when the OH group on carbon 2 (C2) is in the axial position. It was later proposed by Angyal that the Δ2 effect could be cancelled by the presence of an axial OH on C3, termed here the “C3 effect.” Employing size‐exclusion chromatography, an entropically‐controlled separation technique, we have investigated whether or not the C3 and Δ2 effects indeed do compensate for one another with respect to their influence on the solution flexibility of select aldohexoses and aldopentoses. As will be seen, while qualitatively and semiquantitatively this mutual cancellation of effects does occur in aldohexoses, it does not appear to do so in aldopentoses. An explanation for the latter appears to lie in the variety of anomers and conformers present in equilibrium solutions of those aldopentoses studied and in the relative entropic contribution of individual conformers or anomers to the total solution flexibility. © 2013 Wiley Periodicals, Inc. Biopolymers 101: 703–711, 2014.
Barriers, regulations and solutions in emergency surgery research
Authors: Coats T J
Published: November 2013

Time for the surgical community to embrace research in this area
Smartphones make smarter surgeons
Authors: Lewis T L , Vohra R S
Published: November 2013

Time for surgeons to get involved
Anastomoses between lower cranial and upper cervical nerves
Authors: Shoja Mohammadali M. , Oyesiku Nelson M. , Griessenauer Christoph J. , Radcliff Virginia , Loukas Marios , Chern Joshua J. , Benninger Brion , Rozzelle Curtis J. , Shokouhi Ghaffar , Shane Tubbs R.
Published: November 2013

Descriptions of the anatomy of the neural communications among the cranial nerves and their branches is lacking in the literature. Knowledge of the possible neural interconnections found among these nerves may prove useful to surgeons who operate in these regions to avoid inadvertent traction or transection. We review the literature regarding the anatomy, function, and clinical implications of the complex neural networks formed by interconnections among the lower cranial and upper cervical nerves. A review of germane anatomic and clinical literature was performed. The review is organized in two parts. Part I concerns the anastomoses between the trigeminal, facial, and vestibulocochlear nerves or their branches with any other nerve trunk or branch in the vicinity. Part II concerns the anastomoses among the glossopharyngeal, vagus, accessory and hypoglossal nerves and their branches or among these nerves and the first four cervical spinal nerves; the contribution of the autonomic nervous system to these neural plexuses is also briefly reviewed. Part I is presented in this article. An extensive anastomotic network exists among the lower cranial nerves. Knowledge of such neural intercommunications is important in diagnosing and treating patients with pathology of the skull base. Clin. Anat. 27:118–130, 2014. © 2013 Wiley Periodicals, Inc.
A comprehensive review with potential significance during skull base and neck operations, Part II: Glossopharyngeal, vagus, accessory, and hypoglossal nerves and cervical spinal nerves 1–4
Authors: Shoja Mohammadali M. , Oyesiku Nelson M. , Shokouhi Ghaffar , Griessenauer Christoph J. , Chern Joshua J. , Rizk Elias B. , Loukas Marios , Miller Joseph H. , Tubbs R. Shane
Published: November 2013

Knowledge of the possible neural interconnections found between the lower cranial and upper cervical nerves may prove useful to surgeons who operate on the skull base and upper neck regions in order to avoid inadvertent traction or transection. We review the literature regarding the anatomy, function, and clinical implications of the complex neural networks formed by interconnections between the lower cranial and upper cervical nerves. A review of germane anatomic and clinical literature was performed. The review is organized into two parts. Part I discusses the anastomoses between the trigeminal, facial, and vestibulocochlear nerves or their branches and other nerve trunks or branches in the vicinity. Part II deals with the anastomoses between the glossopharyngeal, vagus, accessory and hypoglossal nerves and their branches or between these nerves and the first four cervical spinal nerves; the contribution of the autonomic nervous system to these neural plexuses is also briefly reviewed. Part II is presented in this article. Extensive and variable neural anastomoses exist between the lower cranial nerves and between the upper cervical nerves in such a way that these nerves with their extra‐axial communications can be collectively considered a plexus. Clin. Anat. 27:131–144, 2014. © 2013 Wiley Periodicals, Inc.
Interactive learning management system to develop spatial visualization abilities
Authors: Melgosa Pedrosa Carlos , Ramos Barbero Basilio , Baños García M. Esther
Published: November 2013

An Interactive Learning Management System (ILMS) is presented, which functions as a web‐based Spatial Visualization Ability (SVA) learning support tool for students of engineering graphics and as a management tool for teachers to track student learning. This software is designed to fill the gaps in student knowledge, giving them more uniform spatial visualization abilities when enrolling on University Engineering degrees. The ILMS_SVA consists of: (1) a Content Management System (CMS); (2) a preliminary level assessment test; (3) a web‐based tool for exercise management and self‐assessment incorporating a 3D viewer that functions as an interactive tutorial (IT), allowing the manipulation of 3D objects in every exercise; (4) a database. It is designed for three types of users (student, teacher, and administrator), and has been validated with engineering graphics students at the University of Burgos (Spain) by means of experimental trials in the classroom and a user satisfaction survey, over two academic years. The results indicate that use of this tool improved SVA among students generally and was even of greater effectiveness for those students that accessed engineering courses with no prior knowledge of Technical Drawing. © 2013 Wiley Periodicals, Inc. Comput Appl Eng Educ 23:203–216, 2015; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21590
Biosynthesis of Hygrocins, Antitumor Naphthoquinone Ansamycins Produced by Streptomyces sp. LZ35
Authors: Li Shanren , Wang Haoxin , Li Yaoyao , Deng Jingjing , Lu Chunhua , Shen Yan , Shen Yuemao
Published: November 2013

Hygrocins are naphthoquinone ansamycins with significant antitumor activities. Here, we report the identification and characterization of the hygrocin biosynthetic gene cluster (hgc) in Streptomyces sp. LZ35. A biosynthetic pathway is proposed based on bioinformatics analysis of the hgc genes and intermediates accumulated in selected gene disruption mutants. One of the steps during the biosynthesis of hygrocins is a Baeyer–Villiger oxidation between C5 and C6, catalyzed by luciferase‐like monooxygenase homologue Hgc3. Hgc3 represents the founding member of a previously uncharacterized family of enzymes acting as Baeyer–Villiger monooxygenases.
High dose statin loading prior to percutaneous coronary intervention decreases cardiovascular events: A meta‐analysis of randomized controlled trials
Authors: Benjo Alexandre M. , El‐Hayek Georges E. , Messerli Franz , DiNicolantonio James J. , Hong Mun K. , Aziz Emad F. , Herzog Eyal , Tamis‐Holland Jacqueline E.
Published: November 2013

Objective

We performed a meta‐analysis of randomized controlled trials of statin loading prior to percutaneous coronary intervention (PCI).

Background

Statin loading prior to PCI has been shown to decrease peri‐procedural myocardial infarction (pMI) but less is known regarding the clinical benefit of pre‐procedural statin loading.

Methods

We searched for trials of statin naïve patients presenting with stable angina or NSTE‐ACS and treated with statins prior to PCI. We evaluated the incidence of pMI and major cardiac events including spontaneous myocardial infarction, death, and target vessel revascularization.

Results

Out of 1,210 articles, 14 randomized controlled trials were included in this meta‐analysis. Among 3,146 patients, 1,591 patients were randomized to a loading dose of statin before PCI and 1,555 patients were given statin therapy initiated only after the PCI. Statin loading prior to PCI was associated with a 56% relative reduction in pMI (OR: 0.44, 95% CI: 0.35–0.56; P < 0.00001). There was a 41% reduction in clinical events in follow‐up in the group of patients treated with statin loading prior to PCI (OR: 0.59, 95% CI: 0.38–0.92, P = 0.02). When stratified according to the clinical presentation, the results were only significant for those patients with NSTE‐ACS (OR: 0.18, 95% CI: 0.07–0.47; P = 0.0005) and was not noted in the group of patients who underwent PCI for stable angina (OR: 0.92, 95% CI: 0.53–1.61; P = 0.78).

Conclusions

High dose statin therapy given prior to PCI in patients with NSTE‐ACS is associated with a reduction in pMI and short‐term clinical events. © 2013 Wiley Periodicals, Inc.
Study of Homologous Elements: Fe, Co, and Ni Dopant Effects on the Photoreactivity of TiO2 Nanosheets
Authors: Sun Lei , Zhai Jiali , Li Haiyan , Zhao Yan , Yang Hongjun , Yu Hongwen
Published: November 2013

Despite sustained effort over the years, additional investigations into the relationship between doping elements and the photocatalytic properties of TiO2 are needed. In this work, Fe‐group(Fe, Co, Ni)‐doped anatase TiO2 nanosheets with exposed {0 0 1} facets are prepared by using a facile solvothermal synthetic route. A change in the type and concentration of the doping element consequently leads to a change in the size and percentage of {0 0 1} facets in the TiO2 nanosheets, and finally causes a significant difference in the photocatalytic activities of the as‐prepared TiO2 samples. In this case, the performance of doped TiO2, which serves as the photocatalyst, is investigated by directly assessing its effect on the photodegradation of azo dyes (methylene blue) under UV and visible light irradiation, respectively. Importantly, for the first time these studies reveal that the order of the activities of the doped TiO2 is Ni>Co>Fe, and the optimal value of the percentage of the doping ions to Ti ions is 0.75 %. Electrochemical impedance spectra, photocurrent, and photoluminescence measurements indicate that the charge separation and transportation rate is mainly influenced by the type and concentration of doping ions, which determines the photodegradation activities of the TiO2 host.
Towards the Core Structure of Strychnos Alkaloids Using Samarium Diiodide‐Induced Reactions of Indole Derivatives
Authors: Beemelmanns Christine , Gross Steffen , Reissig Hans‐Ulrich
Published: November 2013

This report describes the development of a first and second generation approach towards the synthesis of the ABCEG pentacyclic core structure of Strychnos alkaloids. First, we discuss a sequential approach applying a series of functional group transformations to prepare suitable precursors for cyclization reactions. These include attempts of samarium diiodide‐induced cyclizations or a Barbier‐type reaction of a transient lithium organyl, which successfully led to a tetracyclic key building block earlier used for the synthesis of strychnine. Secondly, we account our first steps towards the development of an atom‐economical samarium diiodide‐induced cascade reaction using “dimeric” indolyl ketones as cyclization precursors. In this context, we discuss plausible mechanisms for the samarium diiodide‐induced cascade reaction as well as transformations of the obtained tetracyclic dihydroindoline derivatives.
Increased Halide Recognition Strength by Enhanced Intercomponent Preorganisation in Triazolium Containing [2]Rotaxanes
Authors: White Nicholas G. , Costa Paulo J. , Carvalho Sílvia , Félix Vítor , Beer Paul D.
Published: November 2013

Three triazolium‐based [2]rotaxanes containing different sized axle and macrocycle components were synthesised in good yields (40–57 %) through chloride anion templation. The anion recognition properties of the interlocked receptor systems were investigated using 1H NMR titration experiments: all three rotaxanes display impressive selectivities for halide anions over the more basic oxoanion acetate. The rotaxanes incorporating shorter, more rigid axle components with aryl‐substituted triazolium groups display substantially higher anion binding affinities than those with longer, bis‐alkyl‐substituted heterocycles, which is attributed to the increased intercomponent preorganisation afforded by the smaller axle component. Computational DFT and molecular dynamics simulations composed of unconstrained and umbrella sampling simulations corroborate the experimental observations.
Identification of the Chromophore in the Apatite Pigment [Sr10(PO4)6(CuxOH1−x−y)2]: Linear OCuO− Featuring a Resonance Raman Effect, an Extreme Magnetic Anisotropy, and Slow Spin Relaxation
Authors: Kazin Pavel E. , Zykin Mikhail A. , Zubavichus Yan V. , Magdysyuk Oxana V. , Dinnebier Robert E. , Jansen Martin
Published: November 2013

A new chromophore has been identified in copper‐doped apatite pigments having the general composition [Sr10(PO4)6(CuxOH1−x−y)2], in which x=0.1, 0.3 and y=0.01–0.42. By using X‐ray absorption spectroscopy, low‐temperature magnetization measurements, and synchrotron X‐ray powder structure refinement, it has been shown that the oxygenated compounds contain simultaneously diamagnetic Cu1+ and paramagnetic Cu3+ with S=1. Cu3+ is located at the same crystallographic position as Cu1+, being linearly coordinated by two oxygen atoms and forming the OCuO− anion. The Raman spectroscopy study of [A10(PO4)6(CuxOH1−x−y)2,], in which A=Ca, Sr, Ba, reveals resonance bands at 651–656 cm−1 assigned to the symmetric stretching vibration (ν1) of OCuO−. The strontium apatite pigment exhibits a strong paramagnetic anisotropy with an unprecedentedly large negative zero‐field splitting parameter (D) of ≈−400 cm−1. The extreme magnetic anisotropy causes slow magnetization relaxation with relaxation times (τ) up to 0.3 s at T=2 K, which relates the compounds to single‐ion magnets. At low temperature, τ is limited by a spin quantum‐tunneling, whereas at high temperature a thermally activated relaxation prevails with Ueff≈48 cm−1. Strong dependence of τ on the paramagnetic center concentration at low temperature suggests that the spin‐spin relaxation dominates in the spin quantum‐tunneling process. The compound is the first example of a d‐metal‐based single‐ion magnet with S=1, the smallest spin at which an energy barrier arises for the spin flipping.
Exo‐Dig Radical Cascades of Skipped Enediynes: Building a Naphthalene Moiety within a Polycyclic Framework
Authors: Pati Kamalkishore , Hughes Audrey M. , Phan Hoa , Alabugin Igor V.
Published: November 2013

Cascade radical transformations of acyclic precursors open efficient, convenient and atom‐economical access to functionalized compounds of increased structural complexity. This report describes a selective sequence of 5‐exo‐dig and 6‐exo‐dig cyclizations followed by attack at a pendant aromatic moiety and rearomatization.
Potential Risk Assessment of Metal Consumption in Food Crops Irrigated with Wastewater
Authors: Khan Muhammad U. , Muhammad Said , Malik Riffat N.
Published: November 2013

This study investigates the potential risk assessment via consumption of food crops irrigated with wastewater in the districts Sialkot and Gujranwala, Pakistan. For this purpose, samples of water, soil, and food crops were collected from the study area. Metals including potassium (K), sodium (Na), calcium (Ca), magnesium (Mg), copper (Cu), cobalt (Co), iron (Fe), and zinc (Zn) were analyzed using flame atomic absorption spectrophotometry. The concentration of Na was found highest in wastewater (WW), followed by Ca, Mg, etc., while lowest for Co. Similarly, in WW irrigated soil (WWIS) the highest concentration was found for Fe and lowest for Co, while other metal fall between these two extremes. Results showed significance (p < 0.001) using t‐test among WW and WWIS as compared to tube well water (TW) and TW irrigated soil (TWIS). Food crops were assessed for daily intake of metal and health risk index (HRI), revealing an HRI < 1. However, if current practices continued it could cause health hazards in near future. Therefore, this study suggested that local farmers should be educated using awareness programs to avoid WW irrigation to the food crops.
Discovery of 7‐Aryl‐Substituted (1,5‐Naphthyridin‐4‐yl)ureas as Aurora Kinase Inhibitors
Authors: Defaux Julien , Antoine Maud , Le Borgne Marc , Schuster Tilmann , Seipelt Irene , Aicher Babette , Teifel Michael , Günther Eckhard , Gerlach Matthias , Marchand Pascal
Published: November 2013

As part of our research projects to identify new chemical entities of biological interest, we developed a synthetic approach and the biological evaluation of (7‐aryl‐1,5‐naphthyridin‐4‐yl)ureas as a novel class of Aurora kinase inhibitors for the treatment of malignant diseases based on pathological cell proliferation. 1,5‐Naphthyridine derivatives showed excellent inhibitory activities toward Aurora kinases A and B, and the most active compound, 1‐cyclopropyl‐3‐[7‐(1‐methyl‐1H‐pyrazol‐4‐yl)‐1,5‐naphthyridin‐4‐yl]urea (49), displayed IC50 values of 13 and 107 nM against Aurora kinases A and B, respectively. In addition, the selectivity toward a panel of seven cancer‐related protein kinases was highlighted. In vitro ADME properties were also determined in order to rationalize the difficulties in correlating antiproliferative activity with Aurora kinase inhibition. Finally, the good safety profile of these compounds imparts promising potential for their further development as anticancer agents.
Presence of symptom clusters in surgically treated patients with esophageal cancer: Implications for survival
Authors: Wikman Anna , Johar Asif , Lagergren Pernilla
Published: November 2013

BACKGROUND

It is not known whether symptoms cluster together after esophageal cancer surgery or whether such symptom clusters are associated with survival in patients with esophageal cancer who are treated surgically.

METHODS

Data from a prospective Swedish nationwide cohort study of surgically treated patients with esophageal cancer recruited between 2001 and 2005 were used. General and esophageal cancer‐specific symptoms were assessed using the European Organization for Research and Treatment of Cancer QLQ‐C30 quality of life questionnaire and the QLQ‐OES18 module at 6 months after surgery. Associations between symptom clusters and survival were analyzed using Cox proportional hazards models, providing hazards ratios with 95% confidence intervals, adjusted for other known prognostic factors.

RESULTS

Among 402 patients reporting symptoms 6 months after surgery, 3 symptom clusters were identified. The first symptom cluster (“fatigue/pain”) was characterized by symptoms of pain, fatigue, insomnia, and dyspnea and was present in 30% of patients. The second symptom cluster (“reflux/cough”) was characterized by symptoms of dry mouth, problems with taste, coughing, and reflux and was present in 27% of patients. The third symptom cluster (“eating difficulties”) was characterized by appetite loss, dysphagia, eating difficulties, and nausea/vomiting and was present in 28% of patients. The presence of the reflux/cough and eating difficulties symptom clusters was associated with a statistically significantly increased risk of mortality (adjusted hazards ratio, 1.43 [95% confidence interval, 1.08‐1.89] and adjusted HR, 1.41 [95% confidence interval, 1.06‐1.87], respectively).

CONCLUSIONS

Symptoms experienced by surgically treated patients with esophageal cancer appear to cluster together, and the presence of these symptom clusters appears to have strong prognostic value. Cancer 2014;120:286–293. © 2013 American Cancer Society.
Hippocampal neuropathology of domoic acid–induced epilepsy in California sea lions (Zalophus californianus)
Authors: Buckmaster Paul S. , Wen Xiling , Toyoda Izumi , Gulland Frances M.D. , Van Bonn William
Published: November 2013

California sea lions (Zalophus californianus) are abundant human‐sized carnivores with large gyrencephalic brains. They develop epilepsy after experiencing status epilepticus when naturally exposed to domoic acid. We tested whether sea lions previously exposed to DA (chronic DA sea lions) display hippocampal neuropathology similar to that of human patients with temporal lobe epilepsy. Hippocampi were obtained from control and chronic DA sea lions. Stereology was used to estimate numbers of Nissl‐stained neurons per hippocampus in the granule cell layer, hilus, and pyramidal cell layer of CA3, CA2, and CA1 subfields. Adjacent sections were processed for somatostatin immunoreactivity or Timm‐stained, and the extent of mossy fiber sprouting was measured stereologically. Chronic DA sea lions displayed hippocampal neuron loss in patterns and extents similar but not identical to those reported previously for human patients with temporal lobe epilepsy. Similar to human patients, hippocampal sclerosis in sea lions was unilateral in 79% of cases, mossy fiber sprouting was a common neuropathological abnormality, and somatostatin‐immunoreactive axons were exuberant in the dentate gyrus despite loss of immunopositive hilar neurons. Thus, hippocampal neuropathology of chronic DA sea lions is similar to that of human patients with temporal lobe epilepsy. J. Comp. Neurol. 522:1691–1706, 2014. © 2013 Wiley Periodicals, Inc.
Pharmacokinetics and comparative bioavailability of allopurinol formulations in healthy subjects
Authors: Helmy Sally A. , El‐Bedaiwy Heba M.
Published: November 2013

Allopurinol is the most commonly used urate‐lowering therapy in gout. This study was undertaken to evaluate the pharmacokinetics and relative bioavailability of two brands of allopurinol tablets. The in vivo study was established according to a single‐center, randomized, single‐dose, laboratory‐blinded, Two Way, Cross‐Over Study with a washout period of 1 week. Under fasting conditions, 24 healthy male volunteers were randomly allocated to receive a single oral dose (200 mg) of either test and reference formulations. Plasma samples were obtained over a 6‐hour interval and analyzed for allopurinol by reversed phase liquid chromatography with ultraviolet detection. The 90% confidence intervals for the ratio of log transformed values of Cmax, AUC0–t, and AUCt–∞ of the two treatments were within the acceptable range (0.8–1.25) for bioequivalence. From PK perspectives, the two allopurinol formulations were considered bioequivalent, based on the rate and extent of absorption. No adverse events occurred or were reported after a single 200‐mg allopurinol and both formulations were well tolerated.
Indenyl Effect Due to Metal Slippage? Computational Exploration of Rhodium‐Catalyzed Acetylene [2+2+2] Cyclotrimerization
Authors: Orian Laura , Swart Marcel , Bickelhaupt F. Matthias
Published: November 2013

The mechanism of CpRh (Cp=cyclopentadienyl) and IndRh (Ind=indenyl)‐catalyzed acetylene [2+2+2] cyclotrimerization has been revisited aiming at finding an explanation for the better performance of the latter catalyst found experimentally. The hypothesis that an ancillary ligand of the precatalyst remains bonded to the metal center throughout the whole catalytic cycle, based on the experimental evidence that the nature of this ligand can exert some control in cocyclotrimerization of different alkynes, is considered. Strong hapticity variations occur in both the CpRh‐ and IndRh‐catalyzed processes. As the Ind ligand undergoes a more facile slippage than Cp, the energy profile is far smoother in the IndRh‐catalyzed cyclotrimerization. This difference in the energetics of the process translates into an enhanced activity of the IndRh catalyst, in nice agreement with experiment.
Reduction Mechanism of Fluoroethylene Carbonate for Stable Solid–Electrolyte Interphase Film on Silicon Anode
Authors: Chen Xilin , Li Xiaolin , Mei Donghai , Feng Ju , Hu Mary Y. , Hu Jianzhi , Engelhard Mark , Zheng Jianming , Xu Wu , Xiao Jie , Liu Jun , Zhang Ji‐Guang
Published: November 2013

Fluoroethylene carbonate (FEC) is an effective electrolyte additive that can significantly improve the cycling ability of silicon and other anode materials. However, the fundamental mechanism of this improvement is still not well understood. Based on the results obtained from 6Li NMR and X‐ray photoelectron spectroscopy studies, we propose a molecular‐level mechanism for how FEC affects the formation of solid electrolyte interphase (SEI) film: 1) FEC is reduced through the opening of the five‐membered ring leading to the formation of lithium poly(vinyl carbonate), LiF, and some dimers; 2) the FEC‐derived lithium poly(vinyl carbonate) enhances the stability of the SEI film. The proposed reduction mechanism opens a new path to explore new electrolyte additives that can improve the cycling stability of silicon‐based electrodes.
Size‐ and Shape‐Controlled Synthesis of Hexagonal Bipyramidal Crystals and Hollow Self‐Assembled Al‐MOF Spheres
Authors: Sarawade Pradip , Tan Hua , Anjum Dalaver , Cha Dongkyu , Polshettiwar Vivek
Published: November 2013

We report an efficient protocol for the synthesis of monodisperse crystals of an aluminum (Al)‐based metal organic framework (MOF) while obtaining excellent control over the size and shape solely by tuning of the reaction parameters without the use of a template or structure‐directing agent. The size of the hexagonal crystals of the Al‐MOF can be selectively varied from 100 nm to 2000 nm by simply changing the reaction time and temperature via its nucleation‐growth mechanism. We also report a self‐assembly phenomenon, observed for the first time in case of Al‐MOF, whereby hollow spheres of Al‐MOF were formed by the spontaneous organization of triangular sheet building blocks. These MOFs showed broad hysteresis loops during the CO2 capture, indicating that the adsorbed CO2 is not immediately desorbed upon decreasing the external pressure and is instead confined within the framework, which allows for the capture and subsequent selective trapping of CO2 from gaseous mixtures.
Referenced Capacitively Coupled Conductivity Detector for Capillary Electrophoresis
Authors: Stojkovic Marko , Schlensky Boris , Hauser Peter C.
Published: November 2013

A dual capacitively coupled contactless conductivity detector for capillary electrophoresis was developed. The two channels are arranged in a bridge configuration so that one of them acts as a reference whose signal is subtracted. This effectively compensates for the baseline conductivity of the separation buffer so that the electronic zero setting is not necessary. Changes in the buffer composition are automatically accounted for, as are temperature drifts. The system is demonstrated for the detection of inorganic model cations in capillary electrophoresis. Besides the use with two separate capillaries, one of which solely serves as reference, it was also found possible to use a single capillary which is looped back through the reference cell.
An immunoproteomic approach for characterization of the outer membrane proteins of Salmonella Gallinarum
Authors: Cho Youngjae , Sun Jisun , Han Jang Hyuck , Jang Joo Hyun , Kang Zheng Wu , Hahn Tae‐Wook
Published: November 2013

Salmonella enterica serovar Gallinarum (SG) is an important pathogen that causes fowl typhoid in chickens. In order to investigate SG outer membrane proteins (OMPs) as potential vaccine candidate proteins, we established a proteomic map and database of antigenic SG‐OMPs. A total of 174 spots were detected by 2DE. Twenty‐two antigen‐reactive spots were identified as nine specific proteins using PMF. OmpA was the most abundant protein among all of the identified OMPs, and it exhibited seven protein species. We conducted Western blot analysis for the SG‐OMPs in order to determine which proteins were cross‐reactive to the serovars Salmonella Enteritidis, Salmonella Typhimurium, and SG. Our results indicated that OmpA was considered to be an antigenic cross‐reactive protein among the three serovars. This study sheds new light on our understanding of cross‐protection among Salmonella serovars.
Large‐volume sample stacking with polarity switching for monitoring of nucleotide pyrophosphatase/phosphodiesterase 1 (NPP1) reactions by capillary electrophoresis
Authors: Lee Sang‐Yong , Müller Christa E.
Published: November 2013

Nucleotide pyrophosphatase/phosphodiesterase 1 (NPP1) is a membrane glycoprotein involved in the hydrolysis of extracellular nucleotides. Its main substrate is ATP yielding AMP and pyrophosphate. NPP1 has been proposed as a novel drug target, for diabetes type 2 and the treatment of calcium pyrophosphate dihydrate deposition disease leading to inflammatory arthritis. The monitoring of NPP1 reactions is difficult because its velocity is very slow requiring highly sensitive analytical procedures. In this study, a method of large‐volume sample stacking with polarity switching was developed, and separations were optimized. Large sample volumes were loaded by hydrodynamic injection (5 psi, 13 s) followed by removal of a large plug of sample matrix from the capillary using polarity switching (−10 kV). The stacked analytes were subsequently separated in phosphate buffer (100 mM, pH 9.2) at 20 kV. The validated method was found to be linear (R2 = 0.9927) in the concentration range of 0.05–50 μM of AMP, with high accuracy and precision. The determined LOD and LOQ of AMP were 18 nM and 60 nM, respectively. Compared to a previously reported CE procedure using sweeping technique, a fivefold improvement of sensitivity was achieved. Moreover, the new technique was faster, and reproducibility of migration times was improved (RSD value = 1.2%). Importantly, adenine nucleotide analogs and derivatives tested as NPP1 inhibitors could be completely separated from the substrate ATP and the enzymatic product AMP. The method was applied to NPP1 inhibition assays investigating nucleotide‐derived inhibitors in the presence of ATP.