bluuebunny/crossref_metadata_2025 huggingface dataset:
Diagnosis of Van den Ende–Gupta syndrome: Approach to the Marden–Walker‐like spectrum of disorders
Authors: Niederhoffer Karen Y. , Fahiminiya Somayyeh , Eydoux Patrice , Mawson John , Nishimura Gen , Jerome‐Majewska Loydie A. , Patel Millan S.
Published: July 2016

Marden–Walker syndrome is challenging to diagnose, as there is significant overlap with other multi‐system congenital contracture syndromes including Beals congenital contractural arachnodactyly, D4ST1‐Deficient Ehlers–Danlos syndrome (adducted thumb‐clubfoot syndrome), Schwartz–Jampel syndrome, Freeman–Sheldon syndrome, Cerebro‐oculo‐facio‐skeletal syndrome, and Van den Ende–Gupta syndrome. We discuss this differential diagnosis in the context of a boy from a consanguineous union with Van den Ende–Gupta syndrome, a diagnosis initially confused by the atypical presence of intellectual disability. SNP microarray and whole exome sequencing identified a homozygous frameshift mutation (p.L870V) in SCARF2 and predicted damaging mutations in several genes, most notably DGCR2 (p.P75L) and NCAM2 (p.S147G), both possible candidates for this child's intellectual disability. We review distinguishing features for each Marden–Walker‐like syndrome and propose a clinical algorithm for diagnosis among this spectrum of disorders. © 2016 Wiley Periodicals, Inc.
Neutrale Dibor‐Analoga von archetypischen aromatischen Verbindungen durch spontane Cycloaddition
Authors: Arrowsmith Merle , Böhnke Julian , Braunschweig Holger , Celik Mehmet Ali , Claes Christina , Ewing William C. , Krummenacher Ivo , Lubitz Katharina , Schneider Christoph
Published: July 2016

Unter der Vielzahl an Methoden, die Organiker zur Synthese von Benzolderivaten und Heteroarenen entwickelt haben, stellt die übergangsmetallkatalysierte Cycloaddition die eleganteste dar. Dagegen laufen Cycloadditionen mit schweren Alken‐ und Alkin‐Analoga, wenn auch in ihrem Umfang beschränkt, unkatalysiert ab. Hier stellen wir die ersten Cycloadditionen von leichten Alken‐ und Alkin‐Analoga vor, die spontan verlaufen. Die selektive Addition von unaktivierten Alkinen an Bor‐Bor‐Mehrfachbindungen führt unter normalen Bedingungen zu Dibor‐Kohlenstoff‐Äquivalenten von einfachen aromatischen Kohlenwasserstoffen, einschließlich der ersten neutralen, 6 π‐aromatischen Diborabenzol‐Verbindung, einem 2 π‐aromatischen, biradikalischen Triplett‐1,3‐Diboret und einem Phosphan‐stabilisierten 2 π‐homoaromatischen 1,3‐Dihydro‐1,3‐Diboret. Aufgrund der Ähnlichkeit der Grenzorbitale mit analogen aromatischen (C6H6 und C4H42+) und homoaromatischen (C4H5+) Kohlenwasserstoffen deuten DFT‐Rechnungen darauf hin, dass alle drei Verbindungen aromatisch sind.
Neutral Diboron Analogues of Archetypal Aromatic Species by Spontaneous Cycloaddition
Authors: Arrowsmith Merle , Böhnke Julian , Braunschweig Holger , Celik Mehmet Ali , Claes Christina , Ewing William C. , Krummenacher Ivo , Lubitz Katharina , Schneider Christoph
Published: July 2016

Among the numerous routes organic chemists have developed to synthesize benzene derivatives and heteroaromatic compounds, transition‐metal‐catalyzed cycloaddition reactions are the most elegant. In contrast, cycloaddition reactions of heavier alkene and alkyne analogues, though limited in scope, proceed uncatalyzed. In this work we present the first spontaneous cycloaddition reactions of lighter alkene and alkyne analogues. Selective addition of unactivated alkynes to boron–boron multiple bonds under ambient conditions yielded diborocarbon equivalents of simple aromatic hydrocarbons, including the first neutral 6 π‐aromatic diborabenzene compound, a 2 π‐aromatic triplet biradical 1,3‐diborete, and a phosphine‐stabilized 2 π‐homoaromatic 1,3‐dihydro‐1,3‐diborete. DFT calculations suggest that all three compounds are aromatic and show frontier molecular orbitals matching those of the related aromatic hydrocarbons, C6H6 and C4H42+, and homoaromatic C4H5+.
The Hydrated Excess Proton in the Zundel Cation H5O2+: The Role of Ultrafast Solvent Fluctuations
Authors: Dahms Fabian , Costard Rene , Pines Ehud , Fingerhut Benjamin P. , Nibbering Erik T. J. , Elsaesser Thomas
Published: July 2016

The nature of the excess proton in liquid water has remained elusive after decades of extensive research. In view of ultrafast structural fluctuations of bulk water scrambling the structural motifs of excess protons in water, we selectively probe prototypical protonated water solvates in acetonitrile on the femtosecond time scale. Focusing on the Zundel cation H5O2+ prepared in room‐temperature acetonitrile, we unravel the distinct character of its vibrational absorption continuum and separate it from OH stretching and bending excitations in transient pump‐probe spectra. The infrared absorption continuum originates from a strong ultrafast frequency modulation of the H+ transfer vibration and its combination and overtones. Vibrational lifetimes of H5O2+ are found to be in the sub‐100 fs range, much shorter than those of unprotonated water. Theoretical results support a picture of proton hydration where fluctuating electrical interactions with the solvent and stochastic thermal excitations of low‐frequency modes continuously modify the proton binding site while affecting its motions.
A Bioinspired Synthesis of (±)‐Rubrobramide, (±)‐Flavipucine, and (±)‐Isoflavipucine
Authors: Mizutani Shoma , Komori Kenta , Taniguchi Tohru , Monde Kenji , Kuramochi Kouji , Tsubaki Kazunori
Published: July 2016

A biomimetic synthesis of naturally occurring lactams rubrobramide, flavipucine, and isoflavipucine is described. The key step is a regioselective Darzens reaction between isobutyl glyoxal and an α‐bromo‐β‐ketoamide. The construction of the core tricyclic ring system of rubrobramide was achieved by a cascade reaction in a single step from an α,β‐epoxy‐γ‐lactam. Furthermore, the absolute configuration of naturally occurring (+)‐rubrobramide was determined by vibrational circular dichroism. (±)‐Flavipucine and (±)‐isoflavipucine were synthesized from an epoxyimide, which was prepared by reaction of isobutyl glyoxal with a protected α‐bromo‐β‐ketoamide. Deprotection of the epoxyimide and formation of the pyridone ring gave (±)‐flavipucine, which was converted into (±)‐isoflavipucine by thermal isomerization.
Identification of Indole‐Based Chalcones: Discovery of a Potent, Selective, and Reversible Class of MAO‐B Inhibitors
Authors: Sasidharan Rani , Manju Sreedharannair Leelabaiamma , Uçar Gülberk , Baysal Ipek , Mathew Bijo
Published: July 2016

A series of 11 indole‐based chalcones (IC1–11) with various electron donating and withdrawing groups at the para position of the phenyl ring B were synthesized. All the compounds were tested for their human monoamine oxidase (hMAO)‐A and hMAO‐B inhibitory potencies. Most of the synthesized candidates proved to be potent and selective inhibitors of MAO‐B rather than MAO‐A, with a reversible and competitive mode. Among them, compound IC9 was found to be a potent inhibitor of hMAO‐B with Ki = 0.01 ± 0.005 μM and a selectivity index of 120. It was found to be better than the standard drug, selegiline (hMAO‐B with Ki = 0.20 ± 0.020 μM) with a selectivity index of 30.55. PAMPA assays were carried out for all the compounds in order to evaluate the capacity of the compounds to cross the blood–brain barrier. Moreover, the most potent MAO‐B inhibitor, IC9, was nontoxic at 5 and 25 μM, with 95.20 and 69.17% viable cells, respectively. The lead compound IC9 has an antioxidant property of 1.18 Trolox equivalents by ABTS assay. Molecular modeling studies were performed against hMAO‐B to observe binding site interactions of the lead compound.
Continuous counter‐current chromatography for capture and polishing steps in biopharmaceutical production
Authors: Steinebach Fabian , Müller‐Späth Thomas , Morbidelli Massimo
Published: July 2016

The economic advantages of continuous processing of biopharmaceuticals, which include smaller equipment and faster, efficient processes, have increased interest in this technology over the past decade. Continuous processes can also improve quality assurance and enable greater controllability, consistent with the quality initiatives of the FDA. Here, we discuss different continuous multi‐column chromatography processes. Differences in the capture and polishing steps result in two different types of continuous processes that employ counter‐current column movement. Continuous‐capture processes are associated with increased productivity per cycle and decreased buffer consumption, whereas the typical purity‐yield trade‐off of classical batch chromatography can be surmounted by continuous processes for polishing applications. In the context of continuous manufacturing, different but complementary chromatographic columns or devices are typically combined to improve overall process performance and avoid unnecessary product storage. In the following, these various processes, their performances compared with batch processing and resulting product quality are discussed based on a review of the literature. Based on various examples of applications, primarily monoclonal antibody production processes, conclusions are drawn about the future of these continuous‐manufacturing technologies.
Augmenting Chinese hamster genome assembly by identifying regions of high confidence
Authors: Vishwanathan Nandita , Bandyopadhyay Arpan A. , Fu Hsu‐Yuan , Sharma Mohit , Johnson Kathryn C. , Mudge Joann , Ramaraj Thiruvarangan , Onsongo Getiria , Silverstein Kevin A. T. , Jacob Nitya M. , Le Huong , Karypis George , Hu Wei‐Shou
Published: July 2016

Chinese hamster Ovary (CHO) cell lines are the dominant industrial workhorses for therapeutic recombinant protein production. The availability of genome sequence of Chinese hamster and CHO cells will spur further genome and RNA sequencing of producing cell lines. However, the mammalian genomes assembled using shot‐gun sequencing data still contain regions of uncertain quality due to assembly errors. Identifying high confidence regions in the assembled genome will facilitate its use for cell engineering and genome engineering. We assembled two independent drafts of Chinese hamster genome by de novo assembly from shotgun sequencing reads and by re‐scaffolding and gap‐filling the draft genome from NCBI for improved scaffold lengths and gap fractions. We then used the two independent assemblies to identify high confidence regions using two different approaches. First, the two independent assemblies were compared at the sequence level to identify their consensus regions as ”high confidence regions“ which accounts for at least 78 % of the assembled genome. Further, a genome wide comparison of the Chinese hamster scaffolds with mouse chromosomes revealed scaffolds with large blocks of collinearity, which were also compiled as high‐quality scaffolds. Genome scale collinearity was complemented with EST based synteny which also revealed conserved gene order compared to mouse. As cell line sequencing becomes more commonly practiced, the approaches reported here are useful for assessing the quality of assembly and potentially facilitate the engineering of cell lines.
A Highly Water‐Tolerant Magnesium(II) Coordination Polymer Derived from a Flexible Layered Structure
Authors: Ochi Rika , Noro Shin‐ichiro , Kamiya Yuichi , Kubo Kazuya , Nakamura Takayoshi
Published: July 2016

A two‐dimensional (2D) layered MgII coordination polymer (CP) with a high tolerance for H2O was designed, synthesised, and crystallographically characterised. The synthesis was achieved by the introduction of a flexible 2D layered structure composed of MgII ions and isonicotinate N‐oxide ligands. Owing to its high H2O tolerance, the obtained 2D layered structure has the flexibility to repeatedly adsorb a large amount of H2O associated with interlayer expansion and enable the removal of H2O from a H2O/2‐propanol mixed vapour. These results indicate that the CP could be an excellent dehydrating agent.
Helical Folding Competing with Unfolded Aggregation in Phenylene Ethynylene Foldamers
Authors: Luo Zhouyang , Zhu Ningbo , Zhao Dahui
Published: July 2016

The folding and aggregation behavior of a pair of oligo(phenylene ethynylene) (OPE) foldamers are investigated by means of UV/Vis absorption and circular dichroism spectroscopy. With identical OPE backbones, two foldamers, 1 with alkyl side groups and 2 with triethylene glycol side chains, manifest similar helical conformations in solutions in n‐hexane and methanol, respectively. However, disparate and competing folding and aggregation processes are observed in alternative solvents. In cyclohexane, oligomer 1 initially adopts the helical conformation, but the self‐aggregation of unfolded chains, as a minor component, gradually drives the folding–unfolding transition eventually to the unfolded aggregate state completely. In contrast, in aqueous solution (CH3OH/H2O) both folded and unfolded oligomer 2 appear to undergo self‐association; aggregates of the folded chains are thermodynamically more stable. In solutions with a high H2O content, self‐aggregation among unfolded oligomers is kinetically favored; these oligomers very slowly transform into aggregates of helical structures with greater thermodynamic stability. The folded–unfolded conformational switch thus takes place with the free (nonaggregated) molecules, and the very slow folding transition is due to the low concentration of molecularly dispersed oligomers.
Ferrocenyl Paclitaxel and Docetaxel Derivatives: Impact of an Organometallic Moiety on the Mode of Action of Taxanes
Authors: Wieczorek Anna , Błauż Andrzej , Żal Aleksandra , Arabshahi Homayon John , Reynisson Jóhannes , Hartinger Christian G. , Rychlik Błażej , Plażuk Damian
Published: July 2016

A series of ferrocenyl analogues and derivatives of paclitaxel and docetaxel were synthesised and assayed for their antiproliferative/cytotoxic effects, impact on the cell cycle distribution and ability to induce tubulin polymerisation. The replacement of the 3′‐N‐benzoyl group of paclitaxel with a ferrocenoyl moiety, in particular, led to formation of an analogue that was at least one order of magnitude more potent in terms of antiproliferative activity than the parent compound (IC50 values of 0.11 versus 1.11 μm, respectively), but still preserved the classical taxane mode of action, that is, microtubule stabilisation leading to mitotic arrest. Molecular docking studies revealed an unexpected binding pocket in the tubulin structure for the ferrocenoyl group introduced in the paclitaxel backbone.
Detection of Benzene and Alkylated Benzene Derivatives in Fuel Contaminated Environments
Authors: DiScenza Dana J. , Verderame Molly , Levine Mindy
Published: July 2016

Reported herein is the sensitive and selective detection of benzene and alkylated benzene derivatives as well as the practical application of this system in the detection of fuel contaminated environments following a March 2015 tanker truck crash at the Bourne Rotary in Bourne, Massachusetts. This detection method relies on the ability of cyclodextrin to promote proximity‐induced fluorescence modulation of a high quantum yield fluorophore, which led to unique modulation responses for each cyclodextrin‐analyte‐fluorophore combination investigated. The measured changes in fluorescence emission were used to generate arrays using linear discriminant analysis to generate unique pattern identifiers for each combination. The method was successful in detecting ppm levels of analytes with 100% success in differentiating analytes in purified buffer solution and 100% success in differentiating between analytes in water samples from three collection locations related to the crash site: downstream, upstream, and directly from the drainage pipe. Notably, this method was successful in generating well‐separated signals for structural isomers of xylene (ortho, meta, para) which is difficult without specialized mass spectrometry‐based techniques. The high selectivity, sensitivity, and broad applicability of this method have significant potential in the detection of aromatic analytes in a wide range of complex environments.
Chemoselective Synthesis of Carbamates using CO2 as Carbon Source
Authors: Riemer Daniel , Hirapara Pradipbhai , Das Shoubhik
Published: July 2016

Synthesis of carbamates directly from amines using CO2 as the carbon source is a straightforward and sustainable approach. Herein, we describe a highly effective and chemoselective methodology for the synthesis of carbamates at room temperature and atmospheric pressure. This methodology can also be applied to protect the amino group in amino acids and peptides, and also to synthesize important pharmaceuticals.
Statistical Analysis of Particle Flux Flowing into the End‐Target in between Attached and Detached States in the Linear Divertor Plasma Simulator NAGDIS‐II
Authors: Tanaka H. , Ohno N. , Onda T. , Takeyama K. , Kajita S. , Kuwabara T. , Tsuji Y.
Published: July 2016

We have investigated the particle flux flowing into the axisymmetric end‐target in the transient state from attached to detached divertor conditions in the linear plasma device NAGDIS‐II. In the transient state, a dramatic decrease of the mean particle flux and a large‐amplitude fluctuation with negative and positive spikes were observed. We have analyzed the fluctuation with a newly suggested analysis technique: pre‐multiplied cubic spectrum with the wavelet transform. Analysis result indicates that these spikes consist of a few kilohertz components. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Simulation Study of Detached Plasmas by Using One‐Dimensional SOL‐Divertor Fluid Code with Virtual Divertor Model
Authors: Togo S. , Takizuka T. , Nakamura M. , Hoshino K. , Ibano K. , Lang T. L. , Ogawa Y.
Published: July 2016

The detached plasmas due to the volume recombination are studied by using one‐dimensional (1D) scrape‐off‐layer‐divertor (SOL‐DIV) plasma fluid code with virtual divertor (VD) model. By introducing the anisotropic ion temperature, the parallel momentum transport equation becomes the first‐order differential and the Mach number at the sheath entrance is determined self‐consistently by the upstream condition. The total particle flux at the divertor plates and the flux amplification factors are shown as functions of the plasma density at the stagnation point and the dependence of these parameters on the heat flux from the core plasma, radial width of the flux tube in the divetor region and the strength of the impurity radiation is investigated. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Well‐differentiated fetal adenocarcinoma of the lung mimicking adenoid cystic carcinoma on fine needle aspiration: A case report
Authors: Rerkpichaisuth Vilasinee , Collins Jennifer A. , Boonyaarunnate Thiraphon , Ali Syed Z.
Published: July 2016

Well‐differentiated fetal adenocarcinoma (WDFA) of the lung is a rare variant of adenocarcinoma with an unusual morphology. Although the histologic features of this rare neoplasm have been well established, there is a deficit in the literature with regards to its discrete cytomorphologic features. We report the fine needle aspiration (FNA) findings of a case of this unusual malignancy in a 44‐year‐old man with an incidental lung nodule. FNA revealed three‐dimensional clusters of epithelial cells with scant cytoplasm, hyperchromatic nuclei that are associated with an extracellular metachromatic matrix. The original cytology report was signed out as an epithelial neoplasm favor adenoid cystic carcinoma. Consequently, a wedge resection of the lung was done and the histologic diagnosis was WDFA of the lung. The findings of minimal nuclear atypia in association with focally abundant spheres of extracellular matrix can mimic adenoid cystic carcinoma. WDFA has good prognosis and therefore, pre‐operative cytologic diagnosis is critical to clinical management. We present the cytomorphologic features of this neoplasm with particular emphasis on a potential diagnostic pitfall of this rare entity. Diagn. Cytopathol. 2016;44:917–920. © 2016 Wiley Periodicals, Inc.
Steroid pulse therapy was effective for cardiac sarcoidosis with ventricular tachycardia and systolic dysfunction
Authors: Okabe Toshitaka , Yakushiji Tadayuki , Hiroe Michiaki , Oyama Yuji , Igawa Wataru , Ono Morio , Kido Takehiko , Ebara Seitaro , Yamashita Kennosuke , Yamamoto Myong Hwa , Saito Shigeo , Hoshimoto Koichi , Kisaki Amemiya , Isomura Naoei , Araki Hiroshi , Ochiai Masahiko
Published: July 2016

A 32‐year‐old man presented with palpitation. He was diagnosed with pulmonary sarcoidosis by lung biopsy. The electrocardiogram showed first‐degree atrioventricular block and complete right bundle branch block (CRBBB). We planned to examine laboratory data, echocardiography, Holter monitoring, and gallium‐67 scintigraphy. Before he went through all these exams, he developed ventricular tachycardia. After defibrillation was performed, his electrocardiogram revealed complete atrioventricular block. We observed elevation of serum angiotensin‐converting enzyme levels. In addition, both of gallium‐67 scintigraphy and 18F‐fluorodeoxyglucose positron emission tomography showed abnormal uptake in the ventricular septum. We diagnosed the patient with cardiac sarcoidosis associated with these arrhythmias. We started treatment with methylprednisolone pulse therapy (1 g daily). After 3 days of steroid pulse therapy, we administered prednisolone 30 mg daily. On day 15, electrocardiogram changed from complete atrioventricular block to first‐degree atrioventricular block and CRBBB. He was discharged with no progression with cardiac sarcoidosis for 2 years.
The High‐Pressure Polymorph of Ca4Te5O14 and the Mixed‐Valent Compound Ca13TeVI2/3TeIV3.75O15(BO3)4(OH)3
Authors: Weil Matthias , Heymann Gunter , Huppertz Hubert
Published: July 2016

A high‐pressure/high‐temperature experiment based on the multi‐anvil technique has yielded a high‐pressure (HP) modification of Ca4Te5O14 (I) from the starting materials Ca(OH)2 and TeO2. Reaction with the boron nitride crucible used in the high‐pressure set‐up led also to the formation of the mixed‐valent TeIV,VI borate Ca13TeVI2/3TeIV3.75O15(BO3)4(OH)3 (II) as a minor phase. The crystal structures of both compounds were determined by single‐crystal X‐ray diffraction [I: P21/c, Z = 4, a = 11.0272(1), b = 12.0588(1), c = 10.1038(1) Å, β = 91.849(1)°, R1(F2) = 0.0317, wR2(F2) = 0.0459; II: P63/m, Z = 2, a = 9.0890(13), c = 18.731(4) Å, R1(F2) = 0.0401, wR2(F2) = 0.0867]. The principal building units of HP‐Ca4Te5O14, namely [CaOx] (x = 7, 8) and TeIVO3 and TeIVO4 polyhedra, are similar to those of the ambient modification, but the structural set‐up is markedly different in the two structures with an increase in density of about 6.6 %. Ca13TeVI2/3TeIV3.75O15(BO3)4(OH)3 is the first compound known so far to contain both oxotellurate and oxoborate units. The most remarkable feature of its disordered crystal structure is the centrosymmetric Te3O6 unit consisting of a TeVIO6 octahedron sharing opposite faces with two trigonal TeIVO3 pyramids. The face‐sharing of TeVI and TeIV oxopolyhedra is unprecedented in the crystal chemistry of oxotellurates. In both structures I and II, the lone‐electron pairs of the TeIV atoms are stereochemically active.
Acid–Base Behaviour in the Absorption and Emission Spectra of Ruthenium(II) Complexes with Hydroxy‐Substituted Bipyridine and Phenanthroline Ligands
Authors: Yu Fei , Shen Chang , Zheng Tao , Chu Wing‐Kin , Xiang Jing , Luo Ya , Ko Chi‐Chiu , Guo Zheng‐Qing , Lau Tai‐Chu
Published: July 2016

Two bis(2,2′‐bipyridyl)ruthenium(II) complexes bearing hydroxy‐substituted diimine ligands [RuII(bpy)2(N‐N)](BF4)2 (N‐N = phenOH or bpyOH) have been synthesized and characterized. These complexes can be readily deprotonated under basic conditions to yield the deprotonated forms [RuII(bpy)2(N‐N)](BF4) (N‐N = phenO– or bpyO–). The structures of one of the complexes and its deprotonated form have been determined by X‐ray crystallography. The photophysical and electrochemical properties of these complexes have been examined. Detailed photophysical studies showed that the luminescent properties of these complexes are sensitive to the nature of the solvent media. In addition, the emission properties of these complexes exhibit a strong dependence on the pH of the aqueous medium, and hence these complexes are potentially useful as phosphorescent pH probes.
Transition‐Metal Carbonyl Complexes and Electron‐Donating Properties of N‐Heterocyclic‐Carbene–Phosphinidene Adducts
Authors: Bockfeld Dirk , Doddi Adinarayana , Jones Peter G. , Tamm Matthias
Published: July 2016

Rhodium(I), tungsten(0), and molybdenum(0) carbonyl complexes of the N‐heterocyclic‐carbene–phosphinidene adducts IPr·PR [1a, R = H; 1b, R = Ph; 1c, R = Mes; IPr = 1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene; Mes = 2,4,6‐trimethylphenyl] were prepared. The reaction of 1b with [Rh(µ‐Cl)(CO)2]2 afforded the dicarbonyl rhodium(I) complex cis‐[(IPr·PPh)RhCl(CO)2] (2) as the major product together with the tetranuclear complex [{µ‐(IPr·PPh)}2Rh4(µ‐Cl)4(CO)4] (3). The latter was characterized by X‐ray diffraction analysis. The tungsten pentacarbonyl complexes [(IPr·PR)W(CO)5] (4a, R = H; 4b, R = Ph; 4c, R = Mes) were isolated from the reactions of 1a–1c with [(Me3N)W(CO)5], whereas the reactions of 1a and 1b with [(thf)Mo(CO)5] (thf = tetrahydrofuran) gave the corresponding molybdenum complexes [(IPr·PR)Mo(CO)5] (5a, R = H; 5b, R = Ph). The molecular structures of the five carbonyl complexes were established by X‐ray diffraction analyses. The IR spectroscopic analysis of the CO stretching frequencies of the carbonyl complexes 2, 4, and 5 revealed the strong electron‐donating abilities of the phosphorus(I) ligands.
Employment of Voltammetry in Studies of Transport Processes across Artificial Phospholipid Membranes
Authors: Šestáková Ivana , Navrátil Tomáš , Josypčuk Bohdan
Published: July 2016

This paper reports on voltammetric methods applied in studies of transport processes connected with the occurrence of toxic cadmium in plants. As a means of transport across model of phospholipid membrane (PLM), calcium ionophore (calcimycin), cell‐penetrating peptides (transportan 10 and mastoparan), and finally protoplasts isolated from barley roots and leaves were used. Using calcimycin, different influences of Cd complexation by citric acid or by malic acid as examples of root exudates were documented. For transport of simplest phytochelatin PC2, voltammetric methods using formation of Hg complex on hanging mercury drop electrode (HMDE) or of Ag complex on mercury meniscus covered silver solid amalgam electrode (m‐AgSAE) were assessed.
Analysis of a Two‐Stage Fuel Reactor System for the Chemical‐Looping Combustion of Lignite and Bituminous Coal
Authors: Haus Johannes , Lyu Kai , Hartge Ernst‐Ulrich , Heinrich Stefan , Werther Joachim
Published: July 2016

To investigate the influence of the fuel characteristics on the conversion behavior in a chemical‐looping combustion facility, lignite coal dust (d90,3=233 μm) and two fractions of bituminous coal with different particle sizes (fine fraction d90,3=163 μm, coarse fraction d50,3=707 μm) were used as solid fuel. To improve the conversion performance, a pilot plant with a rated power of 25 kW was constructed with a two‐stage fuel reactor. The influence of the fuel composition, particle size, and the presence/absence of elemental oxygen on the conversion in the fuel reactor are presented. The used oxygen carrier was produced by the impregnation of γ‐alumina oxide with copper oxide, which is able to release gaseous oxygen, but loses this ability because of deactivation. The lignite dust shows a very good conversion performance and carbon capture efficiencies over 95 % as well as oxygen demands below 2 %. Both bituminous coal fractions have a good performance with regard to fuel conversion and oxygen demand but they suffer from a high carbon slip. Hence the carbon capture efficiency is around 60 % for the fine fraction and 40 % for the coarse one. The performance improvement as a result of the second stage was investigated separately, and we proved that it enhances the overall conversion. In addition, the oxygen carrier generated a favorable reaction environment by releasing elemental oxygen in the second stage of the fuel reactor.
Management of the clinically N0 neck in squamous cell carcinoma of the maxillary alveolus and hard palate
Authors: Os Alejandra D. van , Karakullukcu Baris , Leemans C. René , Halmos Gyorgy B. , Roodenburg Jan L. N. , Weert Stijn van , Karagozoglu K. Hakki , Witjes Max J. H.
Published: July 2016

Background

The purpose of this study was to evaluate active surveillance strategy in the clinically negative neck in maxillary squamous cell carcinoma (SCC).

Methods

One hundred fourteen consecutive patients diagnosed with oral maxillary SCC were analyzed retrospectively from 3 centers in The Netherlands. Analysis parameters included regional disease‐free survival of N0 patients stratified for T classification, elective radiotherapy (RT) of the neck; and overall survival of the whole cohort, stratified by N classification; salvage neck surgery rates.

Results

Within the N0 cohort, 26.0% of the patients developed neck metastasis in the follow‐up visits. Regional recurrence was not related to T classification or postoperative RT of the neck. Regional and locoregional recurrence were associated with diminished overall survival (p < .05). Regional metastasis was operable in 22 of 26 cases (85%). Only 1 patient presented with inoperable neck metastasis without local recurrence.

Conclusion

Watchful waiting was feasible in this cohort. If meticulous follow‐up is not available, elective neck dissection is recommended. © 2016 Wiley Periodicals, Inc. Head Neck 38: 1794–1798, 2016
Lyciumaside and Lyciumate: A New Diacylglycoside and Sesquiterpene Lactone from Lycium shawii
Authors: Rehman Najeeb Ur , Hussain Hidayat , Al‐Riyami Samia Ahmed , Csuk René , Khiat Mohammed , Abbas Ghulam , Al‐Rawahi Ahmed , Green Ivan R. , Ahmed Ishtiaq , Al‐Harrasi Ahmed
Published: July 2016

One new diacylglycoside named lyciumaside (1) and a new sesquiterpene lactone named lyciumate (2) were isolated from Lycium shawii Roem. & Schult. The structures of the two new compounds were elucidated based on 1D‐ (1H‐ and 13C‐NMR and NOE) and 2D‐NMR (COSY, HSQC, and HMBC) spectroscopic techniques, and mass spectrometry (ESI‐MS). Preliminary evaluations demonstrated lyciumaside (1) possesses strong antioxidant activity with an IC50 = 30 μg/ml (80% inhibition) while it was inactive in α‐glucosidase and urease enzymes assays.
Understanding the foot‐in‐the‐door effect as a pseudo‐effect from the perspective of the Campbell paradigm
Authors: Arnold Oliver , Kaiser Florian G.
Published: July 2016

Compliance with a small request (a metaphorical foot‐in‐the‐door) promotes compliance with a subsequent big request. Whereas some explanations expect a drop in the behavioural costs of the big request, others suspect that the effect comes from boosting the underlying attitude. However, evidence for both explanations is equivocal and circumstantial, at best. Drawing on what Kaiser et al. (2010) call the Campbell paradigm, we present an integrative account: Compliance with any request demands a corresponding attitude to counterbalance the costs of the request. In our research, 229 participants were randomly assigned to either a foot‐in‐the‐door (i.e., initially asked to sign a pro‐environmental petition) or a control condition. Small‐request‐compliant participants were more likely than control participants to also comply with the big request and to continue filling out environmental‐issues‐related questionnaires. However, this foot‐in‐the‐door effect occurred without diminishing behavioural costs or increasing attitude levels. Accordingly, the greater likelihood of small‐request‐compliant participants to also comply with the big request can be parsimoniously explained by baseline variability in people's attitude levels that manifests in their compliance with the initial request. We conclude that several of the foot‐in‐the‐door effects reported in the literature carry the risk of representing mere pseudo‐effects.
Synthesis andin vitrosafety assessment of magnetic bacterial cellulose with porcine aortic smooth muscle cells
Authors: Pastrana Homero F. , Cooper Christy L. , Alucozai Milad , Reece Lisa M. , Avila Alba G. , Allain Jean Paul
Published: July 2016

Bacterial cellulose (BC) has been used as a scaffold for tissue regeneration (TR). Improving functional TR requires highly selective strategies for specific cell attraction. Embedding iron oxide nanoparticles into a BC matrix can drive magnetically labeled cells to specific tissues where they may begin to heal injured tissue. This article focuses on characterization andin vitrotoxicity assessment of magnetic BC (MBC). We proposed to detect the production of radical oxygen species (ROS), esterase activity, and apoptosis to study cytotoxic interactions of MBC within its bioenvironment. Morphological characterization was performed using scanning electron microscopy where evidence shows that the diameter of MBC fibers compared to BC fibers was 33% smaller, and the pore areas were 25% bigger. Cytotoxicity assays in porcine aortic smooth muscle cells exposed for 24 hours to BC, MBC, and poly(ethylene glycol)‐coated MBC (MBC‐PEG) reveals 96% viability and 9% ROS production for MBC‐PEG. In contrast, 25% of cells exposed to MBC were apoptotic, suggesting that even when the cells were metabolically active, MBC can induce damage. These outcomes support the need for more integral assessment in the hopes of assessing the potential biosafety and uses of nanocomposites for TR. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2801–2809, 2016.
Particle size distribution analysis of chemically enhanced two‐phase membrane filtration for olive mill effluents
Authors: Khaligh Sooddeh Salimi , Yagci Nevin , Balcik Cigdem , Ozbey Bahar , Keskinler Bulent , Olmez‐Hanci Tugba , Dizge Nadir , Orhon Derin , Sozen Seval
Published: July 2016

BACKGROUND

This study used particle size distribution (PSD) to reveal how chemical conditioning inflicted changes on different chemical oxygen demand (COD) size fractions to improve the potential of two‐phase membrane separation as an effective preliminary step for the sustainable management of olive processing wastewaters.

RESULTS

Experiments were designed to explore: (i) the potential of membrane separation as a pretreatment step; and (ii) the way in which chemical conditioning improved the removal potential of membrane treatment. Particle size distribution analysis was conducted to observe changes inflicted on different COD size fractions by chemical conditioning. The chemically enhanced membrane process achieved 95% COD removal, reducing the effluent COD to 6000–8000 mg L−1 range and the total phenol down to 100 mg L−1. Chemical conditioning also removed a significant portion of soluble COD, so that the resulting PSD fingerprint in the effluent was properly reshaped to allow effective removal by membrane treatment.

CONCLUSION

The investigated treatment schemes involving pretreatment of oil wastewater by chemical conditioning together with membrane filtration offered high COD reduction in the effluent and biodegradable permeate when properly diluted for co‐treatment with a compatible wastewater stream. The use of chemical conditioning prior to membrane filtration improved final permeate quality and ultrafiltration membrane flux. © 2016 Society of Chemical Industry
Polyelectrolytes–protein complexes: a viable platform in the downstream processes of industrial enzymes at scaling up level
Authors: Woitovich Valetti Nadia , Brassesco M Emilia , Picó Guillermo Alfredo
Published: July 2016

Complexation between proteins and polyelectrolytes through electrostatic interactions gives either soluble or non‐soluble complexes, leading to phase separation. The formation and the stability of these complexes are influenced by pH, ionic strength, ratio between protein and polyelectrolyte and charge density of protein and polyelectrolyte. This review presented the advantages on the protein precipitation by adding a polyelectrolyte solution to a natural enzyme source (microbiological, vegetal or animal homogenate), over the classical precipitation methods. An enzyme can be precipitated like non‐soluble complex, separated and then re‐dissolved, thus the method works, at the same time, like concentrative and pre‐purification steps together. © 2016 Society of Chemical Industry
Process Development through Solvent Engineering in the Biocatalytic Synthesis of the Heterocyclic Bulk Chemical ε‐Caprolactone
Authors: Reimer Anna , Wedde Severin , Staudt Svenja , Schmidt Sandy , Höffer Diana , Hummel Werner , Kragl Udo , Bornscheuer Uwe T. , Gröger Harald
Published: July 2016

For an alternative synthetic approach toward the heterocyclic industrial chemical ε‐caprolactone, which is based on a biocatalytic oxidation of readily available cyclohexanol with air in aqueous media (using an alcohol dehydrogenase and a Baeyer–Villiger monooxygenase as enzyme components), a solvent engineering has been carried out identifying isooctane as a suitable co‐solvent. Biotransformations in an aqueous‐isooctane biphasic solvent system were found to proceed faster at both investigated substrate concentrations of 40 and 80 mm, respectively, compared with the analogous enzymatic reactions in pure aqueous medium. In addition, in all cases quantitative conversions were observed after a reaction time of 23 h when using isolated enzymes. The achievements indicate a high compatibility of isooctane [10%(v/v)] with the enzymes as well as the potential for an in situ removal of the organic reaction components, thus decreasing inhibition and/or destabilization effects of these organic components on the enzymes used. In contrast, so far, the use of recombinant whole‐cells gave less satisfactory results, which might be due to limitations of the permeation of, for example, the substrate through the cell membrane.
In vitro antioxidant activity of rice protein affected by alkaline degree and gastrointestinal protease digestion
Authors: Liu Ye , Wang Zhengxuan , Li Hui , Liang Mingcai , Yang Lin
Published: July 2016

BACKGROUND

To elucidate whether and how alkali treatment, which is a common process for rice protein (RP) extraction, affects antioxidant activity of RP, the different degree of alkali (from 0.1% to 0.4% of NaOH) was used to extract RP (RP‐1, RP‐2, RP‐3, RP‐4).

RESULTS

The antioxidant capacities of scavenging free radicals [2,2′‐azinobis(3‐ethylbenzothiazoline‐6‐sulfonic acid] diammonium salt, ABTS; 1,1‐diphenyl‐2‐picrylhydrazyl, DPPH), chelating metals (iron, copper) and reducing power investigated in the hydrolysates of RPs (RP‐1, RP‐2, RP‐3, RP‐4) during in vitro pepsin–pancreatin digestion were effectively affected by alkali treatment. The present study demonstrated that the weakest antioxidant responses to ABTS radical‐scavenging activity, DPPH radical‐scavenging activity, iron chelating activity, copper chelating activity and reducing power were produced by RP‐4 extracted by the highest alkali proportion (0.4% NaOH).

CONCULSION

The present study indicates that antioxidant capacity of RP could be more readily depressed by strict alkali degree and affected by gastrointestinal proteases. Results suggest that alkali extraction is a vital process to regulate the antioxidant activity of RP through modifying the compositions of amino acids, which are dependent on alkali magnitude. © 2016 Society of Chemical Industry
Black disk visibility, turbidity, and total suspended solids in rivers: A comparative evaluation
Authors: West Amie O. , Scott J. Thad
Published: July 2016

This study compared horizontal black disk visibility (BDV), a measure of visual water clarity, to turbidity and total suspended solids (TSS) concentrations in five rivers of the southwestern Ozarks of Arkansas, U.S. to assess its usefulness in evaluating optical water quality. We investigated correlative relationships between BDV vs. turbidity and BDV vs. TSS, and compared them to those reported in similar studies. Our results indicated that replicate measures of horizontal BDV were subject to less error than replicate turbidity (coefficients of variation were 5.0% and 6.4%, respectively), and BDV was more strongly correlated with TSS concentrations than was turbidity (correlations coefficients were −0.97 and 0.92, respectively). We also assessed the validity of the black disk method as a surrogate for TSS concentrations and derived a predictive model for each river in the study. The benefits of the horizontal black disk method are both scientific and practical. Horizontal BDV provides a means of quantifying the beam attenuation coefficient. And, the low cost, ease of use, and usefulness in shallow rivers make the black disk method a versatile tool in water quality assessment. We ultimately conclude that the horizontal black disk method should be added to routine monitoring programs in the U.S., and that it be adopted by public groups involved in volunteer monitoring and water quality communication that may be limited by equipment availability or budget.
Synthesis of Polyester Dendritic Scaffolds for Biomedical Applications
Authors: Sadowski Lukas P. , Edem Patricia E. , Valliant John F. , Adronov Alex
Published: July 2016

Using a well‐defined poly(2,2‐bis(hydroxymethyl)propanoic acid) dendrimer scaffold, a series of G1 to G3 dendrons is functionalized at the periphery with alkynes to enable “Click” functionalization via the copper‐catalyzed alkyne–azide cycloaddition (CuAAC). The resulting dendrons are further functionalized at the core with a dipicolylamine (DPA) moiety to enable radiolabeling with 99mTc for molecular imaging applications. Efficient CuAAC coupling is achieved using an azide‐functionalized triethylene glycol monomethyl ether (TEG‐N3). Removal of copper from the DPA ligand is successfully performed on G1 and G2 dendrimers prior to radiolabeling with 99mTc. Radiolabeling of the G3 dendrimer is accomplished via transmetallation of the [CuDPA]2+ ligand with 99mTc, further demonstrating the feasibility of the synthetic strategies in the preparation of dendritic imaging agents. Subsequent attachment of an acyloxymethyl ketone (AOMK) derivative for targeting of cathepsin B is also explored. Despite demonstrating the ability to ligate multiple AOMK ligands, the AOMK–dendrimer conjugates are not able to bind to cathepsin B, which may be attributed to steric hindrance at the dendrimer periphery.

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FlowVisor‐based cost‐aware VN embedding in OpenFlow networks
Authors: Zhong Xuxia , Wang Ying , Qiu Xuesong , Li Wenjing
Published: July 2016

Software‐defined network has emerged as a promising network technology to simplify the network management and enable innovation through network programmability. With the help of FlowVisor, network virtualization is achieved in software‐defined networks. We mainly focus on investigating how to embed virtual network requests with different network sizes (small, regular, and large) in a cost‐efficient way. However, the features of FlowVisor and limitations of OpenFlow switches, such as the presence of a central controller, the limited flow space resource, and the out‐of‐band bandwidth requirement, bring new challenges. In this paper, we first formulate the FlowVisor‐enabled cost‐aware virtual network embedding issue as an integer linear programming problem. Then, we propose two embedding algorithms: a heuristic algorithm LF‐OVNE and a meta‐heuristic algorithm CA‐CVNC‐EPSO. Meanwhile, a separate step is taken to select a cost‐aware controller for each slice. Finally, we evaluate our algorithms and compare the embedding performance with the existing algorithms. The simulation results show that our algorithms perform the online virtual network embedding in a more cost‐efficient way. Copyright © 2016 John Wiley & Sons, Ltd.
Preparation and characterization of synergistically improved thermally conductive polyamide 6 with low melting point metal and low‐temperature expandable graphite
Authors: Jia Yunchao , He Hui , Yu Peng , Chen Jian , Tian Shenghui
Published: July 2016

The effects of introduction of low‐temperature expandable graphite (EG) and low melting point metal‐tin (Sn) on the thermal conductivity (TC) of polyamide 6 (PA6) were investigated. After introducing 10 wt% of Sn as single filler, the TC of PA6 was nearly constant, while this value was dramatically increased to 5.187 W (mk)−1 when 10 wt% of Sn was added into PA6/EG(40 wt%). The value was 90.1% higher than that of PA6/EG (40 wt%) composite, and 21.9% higher than that of PA6/EG (50 wt%), which suggested that the incorporation of EG and Sn had significant synergistic effect on the TC improvement of PA6. The electrical conductivity of the composite increased nearly 7 orders of magnitudes at the maximum filler content. Characterization of microstructure and energy spectrum analysis indicated that the dispersion of Sn in PA6/EG/Sn ternary composites was much more uniform than that of PA6/Sn binary composites. Differential scanning calorimetry measurement revealed that the crystalline peaks of Sn in PA6/EG/Sn composites disappeared and new exothermic peaks emerged at higher temperatures, which was mainly ascribed to the interaction between EG sheets and Sn. POLYM. COMPOS., 39:1818–1826, 2018. © 2016 Society of Plastics Engineers
Posterior urethral valves and vesicoureteral reflux: can prenatal ultrasonography distinguish between these two conditions in male fetuses?
Authors: Chitrit Yvon , Bourdon Mathilde , Korb Diane , Grapin‐Dagorno Christine , Joinau‐Zoulovits Félicia , Vuillard Edith , Paye‐Jaouen Annabel , Peycelon Matthieu , Belarbi Nadia , Delezoide Anne‐Lyse , Schmitz Thomas , El Ghoneimi Alaa , Sibony Olivier , Oury Jean‐François
Published: July 2016

Objective

The objective of the study was to evaluate prenatal sonographic signs that distinguish male fetuses with posterior urethral valves (PUV) from those with vesicoureteral reflux (VUR).

Methods

Prenatal data were retrospectively retrieved from all consecutive women delivering between 2003 and 2012 of a male newborn with a postnatal diagnosis of PUV or VUR. Prenatal parameters included fetal bladder characteristics, identification of a dilated posterior urethra, and change in shape and size in the fetal renal pelvis or ureter.

Results

One hundred thirty‐six women gave birth to a male newborn with a postnatal diagnosis of PUV (n = 49) or VUR (n = 87). The presence of posterior urethral dilatation [21 (42.9%) fetuses versus 0 (0%), p = 0.000], a thickened fetal bladder wall [37 (75.5%) vs 4 (4.6%), p = 0.000], and anhydramnios [14 (28.6%) vs 0, p = 0.000] were strongly associated with the postnatal diagnosis of PUV. Change in shape and size in the fetal renal pelvis or ureter was observed in 15 (17.2%) of 87 children with VUR versus 1 (2.0%) out of 49 with PUV (p = 0.010).

Conclusions

Prenatal ultrasound may differentiate with reasonable accuracy male fetuses with a postnatal diagnosis of PUV from those with VUR. © 2016 John Wiley & Sons, Ltd.
Chemistry of polydopamine analogues
Authors: Mrówczyński Radosław , Markiewicz Roksana , Liebscher Jürgen
Published: July 2016

Polydopamine analogues (PDANAs) extend the prospering field of polydopamine (PDA) considerably. They include additional functional groups providing altered properties interesting for various applications. PDANAs can be obtained by post functionalization of PDA, by oxidative polymerization of dopamine derivatives or by copolymerization of dopamine with dopamine derivatives, other monomers or reactive polymers. This review covers the state of the art and gives insight into the huge potential of the field to be explored in the future. © 2016 Society of Chemical Industry