bluuebunny/crossref_metadata_2025 huggingface dataset:
High Diastereoselection of a Dissymmetric Capsule by Chiral Guest Complexation
Authors: Tsunoda Yuta , Fukuta Katsunori , Imamura Taisuke , Sekiya Ryo , Furuyama Taniyuki , Kobayashi Nagao , Haino Takeharu
Published: June 2014

Encapsulation of chiral guests in the dissymmetric capsule 1⋅4 BF4 formed diastereomeric supramolecular complexes G⊂1⋅4 BF4 (G: guest). When chiral guests 2 a–q were encapsulated within the dissymmetric space of the self‐assembled capsule 1⋅4 BF4, circular dichroism (CD) was observed at the absorption bands that are characteristic of the π–π* transition of the bipyridine moiety of the capsule, which suggests that the P and M helicities of the capsule are biased by the chiral guest complexation. The P helicity of diastereomeric complex (S)‐2 l⊂1⋅4 BF4 was determined to be predominant, based on CD exciton coupling theory and DFT calculations. The diastereoselectivity was highly influenced by the ester substituents, such that benzyl ester moieties were good for improving the diastereoselectivity. A diastereomeric excess of 98 % was achieved upon the complexation of 2 j. The relative enthalpic and entropic components for the distereoselectivity were obtained from a van’t Hoff plot. The enthalpic components were linearly correlated with the substituent Hammett parameters (σp+). The electron‐rich benzyl ester moieties generated donor–acceptor π–π stacking interactions with the bipyridine moiety, which resulted in a significant difference in energy between the predominant and subordinate diastereomeric complexes.
Catalytic Paradigms: A Riddle and a Puzzle
Authors: van Santen Rutger A.
Published: June 2014

The perfect catalyst: The advances towards the ability to design a catalyst from first principles are explored. Aspects of computational chemistry as well as the kinetics and physical state of the reactive catalyst are discussed.
Enantioselective Catalysis of the Intermolecular [2+2] Photocycloaddition between 2‐Pyridones and Acetylenedicarboxylates
Authors: Maturi Mark M. , Bach Thorsten
Published: June 2014

Intermolecular [2+2] photocycloadditions represent the most versatile and widely applicable of photochemical reactions. For the first time, such intermolecular reactions have been carried out in a catalytic fashion using a chiral triplet sensitizer, with high enantioselectivity (up to 92 % ee). The low catalyst loading (2.5–5 mol %) underlines the high efficiency of the process both in terms of reaction acceleration and differentiation of the enantiotopic faces of the substrate. The substrate is anchored to the chiral catalyst through noncovalent interactions (hydrogen bonds), thus providing a chiral environment in which the enantioselective photocycloaddition proceeds. The densely functionalized products present numerous possibilities for further synthetic transformations.
Characterization of polyetheretherketone particle suspensions for electrophoretic deposition
Authors: Clavijo Silvia , Membrives Francisco , Boccaccini Aldo R. , Santillán María J.
Published: June 2014

Suspensions of polyetheretherketone (PEEK) using mixture of ethanol and isopropanol as solvent were prepared to carry out PEEK electrophoretic deposition (EPD). The rheological behavior and suspension structure of PEEK particles dispersed in co‐solvents were investigated over a range of pH values (1–10) and shear rates (γ = 101−3 × 102 s−1). These PEEK suspensions generally exhibited a pseudoplastic flow behavior, indicating the occurrence of particle aggregation in the liquid medium. The maximum solids fraction (ϕm) showed an estimated value of  ϕm = 2.9 wt %. Using a suspension with 3 wt % PEEK concentration, PEEK coatings on stainless steel substrates were obtained by EPD at constant voltage condition. The influence of the electrolyte conductivity on PEEK EPD from ethanol–isopropanol suspensions was studied. Experimental results showed that high‐conductivity ethanol‐based suspensions yield non‐uniform deposits, while low‐conductivity suspensions resulted in uniform coatings. The difference in the deposition behavior is due to the different pH of the suspensions and the relationship of pH with suspension conductivity. pH = 8 was the optimal value for this system in terms of deposition results. The surfaces of EPD PEEK coatings were homogenous and a qualitatively good adhesion between the PEEK deposits and the substrate was confirmed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40953.
Applying vermiculite‐modified polypropylene film to flexible packaging material
Authors: Fu YaBo , Li DongLi , Xu WenCai , Qi YingQun , Shang Wei , Wu WeiXia , Wang YaJun
Published: June 2014

This article presents a process for preparing organovermiculite by ball‐milling expanded vermiculite (EVMT) in water‐based ethylene vinyl acetate (EVA) latex. In this process, the vermiculite (VMT) is exfoliated to prepare a kind of EVMT/EVA modifying agent, in which EVA serves as both intercalating polymer into VMT and compatibilizer between VMT and polypropylene (PP). During melt blending between EVMT/EVA and PP, shear force exfoliates VMT sheets, dispersing them relatively well in the PP matrix. Compared with raw PP, EVMT‐modified cast polypropylene (CPP) are better when EVMT loading ranged from 0.5 to 1.0%, with improvement in both the strength and toughness of the EVMT/EVA‐modified CPP film. Specifically, tensile strength was increased by 44–54%, yield stress increased by 26%, stress at break increased by 37–43%, energy at break (toughness) increased by 29–34%, oxygen transmission rate decreased by 6.2–12.9%, the water vapor transmission rate was not significantly affected, the peel bond strength of laminated CPP film increased by 18–27%, and the processability and melt flow index (MFI) of EVMT/EVA/PP composites were improved as well. Increasing MFI attributes facilitated the processing and formation of EVMT/EVA/PP. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40954.
Determination of mass transport properties in food/packaging systems by local measurement with Raman microspectroscopy
Authors: Martinez‐Lopez Brais , Chalier Pascale , Guillard Valerie , Gontard Nathalie , Peyron Stephane
Published: June 2014

A fast, nondestructive method based on the determination of local concentration profiles in the polymer thickness with Raman microspectroscopy is presented here. It was used to assess the diffusivity of a model molecule (p‐terphenyl) in amorphous polystyrene films at 95°C (2.38 ± 1.08 × 10−17 m2/s). This methodology was validated by comparison with a more classical destructive approach based on the monitoring of the concentration evolution in the whole of the film with gas chromatography (89.4 × 10−17 m2/s). These values were in agreement with data available in the literature for molecules of the same molecular weight and temperature range determined with local measurement and were significantly lower than those determined by global measurement. Raman microspectroscopy was found to be adapted to slow diffusion speeds typically found in high‐barrier polymers; this allowed diffusivity to be obtained long before the equilibrium was reached and, thus, without the need for the partition coefficient. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40958.
Recycling of reactive dye using semi‐interpenetrating polymer network from sodium alginate and isopropyl acrylamide
Authors: Dhanapal V. , Subramanian K.
Published: June 2014

A sequence of semi‐interpenetrating polymer network (semi‐IPN) were synthesized by free radical photo copolymerizing acrylic acid and isopropyl acrylamide (NIPAAm) in aqueous sodium alginate (NaAlg). Their structures (FT‐IR), thermal stability (TG/DTG), morphology (SEM), mechanical properties, reactive blue 4 (RB 4) dye adsorption (624 mg/g) and its dying characteristics, reusability of dye and adsorbent were evaluated. TG thermograms of semi‐IPN in air revealed zero order kinetics for initial step thermal degradation with an activation energy of 68.68 kJ/mol. Dye adsorption showed best fit for Langmuir adsorption isotherm and the kinetics followed pseudo‐second‐order model. The water and dye diffusion kinetics followed non‐Fickian mechanism. The changes in thermodynamic parameters namely Gibbs free energy (ΔG°), entropy (ΔS°) and enthalpy (ΔH°) indicated that the adsorption was spontaneous and exothermic process for RB 4/semi‐IPN system. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40968.
Study on the tribological properties of porous sweating PEEK composites under ionic liquid lubricated condition
Authors: Zhu Yanji , Lin Shan , Wang Huaiyuan , Liu Dujuan
Published: June 2014

The tribological behaviors of novel porous Polyetheretherketone (PEEK) composites under 1‐hexyl‐3‐methylimidazolium tetrafluoroborate ionic liquid lubricated condition were investigated. The effect of sliding velocity and applied load on the sweating tribological properties and the stability of lubricating oil film was also studied. Results indicated that when the sliding velocity was 0.69 m/s and the applied load was 250 N, the friction coefficient and wear rate of the ionic liquid lubricated porous sweating activated carbon fiber/polytetrafluoroethene/PEEK composites showed the minimum values, were 0.0197 and 4.145 × 10−15 m3/Nm, respectively. The friction coefficients fluctuated in a narrow range of 0.0162–0.0215. It was found that the porous sweating PEEK composites under ionic liquid lubricated condition showed good low‐friction and antiwear performance, especially under the condition of high sliding velocity and applied load. The formed transfer film due to the tribo‐chemical reaction as well as boundary lubricating film is effective in improving the carrying capacity and antiwear properties of the porous sweating PEEK composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40989.
Kinetic study on free radical grafting of polyethylene with acrylic acid by reactive extrusion
Authors: Zhang Guofang , Zhang Min , Jia Yuxi
Published: June 2014

In the reactive extrusion process for the free radical grafting of acid monomers onto polyethylene, monomer grafting and homopolymerization occur simultaneously and interact with each other. Using an incremental theory, mathematical models of conversions for monomer grafting and homopolymerization were separately constructed to predict the grafting degree, mass of homopolymer and grafting efficiency. Effects of the barrel temperature, initial monomer and initiator concentrations on grafting behaviors were investigated. The barrel temperature and initial monomer concentration were shown to be the main process parameters for controlling the grafting degree. The grafting degree and mass of homopolymer increased significantly with increasing barrel temperature and monomer concentration and increased marginally with increasing initiator concentration. No significant improvement in the grafting efficiency was observed. The predictions of the models are in good agreement with experimental data. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40990.
Effect of orientation and content of carbon based fillers on thermal conductivity of ethylene‐propylene‐diene/filler composites
Authors: Kim Ji‐Hoo , Kim Gue‐Hyun
Published: June 2014

In this study, synthetic graphite, carbon fiber, and carbon nanotube were used as thermal conductive fillers and ethylene‐propylene‐diene (EPDM) as matrix. Oriented EPDM/filler composites were prepared with two‐roll mill, and the effects of orientation and content of carbon based fillers on thermal conductivity and tensile strength of the composites were investigated. Parallel thermal conductivity of the oriented composites is significantly higher than normal thermal conductivity of the oriented composites. Especially, at 31.6% graphite content, parallel thermal conductivity of oriented composites is 7.14 W/mK. Very high thermal conductivity was achieved for oriented EPDM/graphite composites. Orientation of the fillers using two‐roll mill significantly improves the thermal conductivity in the orientation direction. For all the EPDM/filler composites, tensile strength of orientation direction is higher than that of normal direction. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41000.
Die Setzung von Fundamenten auf unterschiedlichen Gründungen mit eingeschränkter Lastausbreitung
Authors: Priebe Heinz J.
Published: June 2014

Die Gründung von Fundamenten lässt sich prinzipiell zwischen dem Grenzfall der ‘flachen’ Gründung auf unbehandeltem Untergrund und dem der ‘tiefen’ auf Pfählen einordnen. Im ersten Fall breitet sich die Spannung aus der gesamten Fundamentlast im Baugrund systematisch aus. Es treten mehr oder weniger große Setzungen auf, die zumindest bei kleinen Fundamenten wegen der Spannungsausbreitung mit der Tiefe verhältnismäßig schnell abklingen. Im zweiten Fall leiten Pfähle fast die gesamte Last in Bodenschichten mit hoher Tragfähigkeit ab. Obwohl es zu keiner nennenswerten entlastenden Spannungsausbreitung kommt, sind die Setzungen dann auch bei hoher Last wegen der großen Pfahlsteifigkeit gering.

Zwischen diesen Grenzfällen gibt es viele Gründungsarten oder –kombinationen, die in ihrem Setzungsverhalten weniger leicht einzuschätzen sind. Sie reichen von der sogenannten Pfahl‐Plattengründung bis zu bodenverbessernden Maßnahmen. In all diesen Fällen konzentriert sich die Lastabtragung auf den bewehrten oder verbesserten Baugrund unter dem Fundament, aber ein mehr oder weniger großer Teil der Fundamentlast wird auch nach außen auf den unbehandelten Boden abgegeben. Dieser abfließende Teil, nachstehend als Lastausbreitung bezeichnet, lässt sich oft schwer bestimmen. Da er aber eine erhebliche Rolle im Hinblick auf das Setzungsverhalten der Gründung spielen kann, wird hiermit ein brauchbares Berechnungsverfahren vorgestellt, das die jeweilige Lastausbreitung näherungsweise berücksichtigt.

The settlement of footings on different kinds of subsoil treatment with reduced load distribution

In principal, the foundation of footings can be ranked between the border case of a shallow foundation on unimproved ground and a deep foundation with piles. In the first case the pressure of the total load spreads systematically in the subsoil. More or less large settlements occur but – at least in the case of small footings – they decrease fairly quickly due to the spreading of the pressure with the depth. In the second case piles transfer the load directly to soil strata with high bearing capacity. Although no notably relieving spreading of pressure occurs settlements are small even at a high load due to the stiffness of the piles.

In between these two cases there are many foundation methods or combinations with settlement performances that cannot easily be evaluated. They range from the so‐called pile‐plate foundation to soil improvement below the foundation. In all these cases the load pressure concentrates on the reinforced or improved subsoil under the foundation. However, either more or less of it is delivered to the untreated soil around. This ”escaping” part, hereinafter called “load distribution” is often difficult to be determined. It may, however, be of substantial importance with regard to the settlement behaviour, so this is to introduce a suitable approximation to consider in a settlement calculation the appropriate load distribution.
Ansatz zur Risserkennung in Stahlblechen anhand der Verzerrung von Lamb‐Wellen
Authors: Wagner Tobias , Unglaub Julian , Thiele Klaus
Published: June 2014

In der hier vorgestellten Arbeit wird die Materialermüdung von Stahlproben anhand der Verzerrung von Lamb‐Wellen untersucht. Gekerbte Stahlproben werden zyklisch auf Zug bis zum Bruch im Low‐Cycle‐Fatigue (LCF) belastet. In Abständen von 1000 Lastzyklen wird die Prüfmaschine angehalten. Ein Aktuator regt Lamb‐Wellen bei einzelnen Frequenzen und Frequenzbändern im Bereich von 1 bis 500 kHz an. Nachdem die Lamb‐Wellen die Kerbe durchlaufen haben, werden sie von einem Sensor aufgenommen. Die Auswertung der gemessenen Spektren zeigt, dass die mittlere Amplitude mit zunehmender Materialermüdung kleiner wird. Diese Ergebnisse bieten die Grundlage zur Entwicklung eines möglichst robusten Verfahrens zur Risserkennung. Ein wesentlicher Vorteil eines solchen Ansatzes ist, dass kurz vor der Entstehung sichtbarer Risse die Materialermüdung erkannt werden kann, ohne dass dafür Referenzmessungen des ungeschädigten Bauwerks nötig sind.

Lamb‐wave distortion as approach to detect cracks in steel plates

The work presented here examines fatigue of steel specimens based on harmonic‐distortion of Lamb‐waves. Cyclic tension load is applied on notched steel specimens until failure under Low‐Cycle‐Fatigue (LCF) occurs. The fatigue test is interrupted every 1000 load cycles. An actuator excites Lamb‐waves with singular frequencies and frequency bands in a range from 1 to 500 kHz. After the Lamb‐waves passed the notch they are recorded by a sensor. Analysing the spectra shows a declining of the average amplitude with increasing material fatigue. These results provide an approach to develop a robust crack detection methodology. A major advantage of such an approach is the ability to detect cracks at least shortly before they become visible without requiring reference measurements of the undamaged structure.
Geodäsie im Investitionsbauprozess auf den Bahngebieten in Polen
Authors: Kampczyk Arkadiusz
Published: June 2014

Der Artikel bezieht sich auf die gegenwärtigen Organisationsstrukturen der Geodäsie und die sie begleitenden organisatorischen Einheiten mit Investitionscharakter auf den Bahngebieten in Polen, die im Investitionsbauprozess von erheblicher Bedeutung sind. Der vorliegende Beitrag erläutert den geltenden Fachwortschatz und die Funktion der Organisationsstrukturen. Es wird dabei hervorgehoben, dass die polnischen Bahngebiete zu den sog. geschlossenen Gebieten gehören. Die Thematik spielt eine wesentliche Rolle im Investitionsprozess für den Bahnverkehr und die Bahninfrastruktur. In den letzten Jahren kamen im Bereich des Bauinvestitionsprozesses für den Bahnverkehr und die Bahninfrastruktur sowie der Funktion der Organisationsstrukturen der Geodäsie, die mit der Gründung der neuen organisatorischen Einheit mit dem Investitionscharakter verbunden war, gravierende Veränderungen zustande. In der vorliegenden Arbeit werden die von dem Autor zusammengestellten Erkenntnisse, Fazits und Anmerkungen zu diesem Aspekt vorgestellt. Der Beitrag entstand im Rahmen der Satzungsuntersuchungen Nr. AGH 11.11.150.005.

Surveying in construction investment process in the areas of railway in Poland

This article applies to current organizational structures of geodesy and its associated units of investment on railway premises in Poland, which play a vital role in building the investment process. Zooms in legal terms and their organizational structures. Attention is drawn to the fact that the railway areas in Poland belong to the so‐called closed areas. This subject plays an important role in the investment process, communication and infrastructure construction. In recent years, Poland experienced a big change in the investment process and transport construction of railway infrastructure and the functioning of the organizational structures of surveying with the appointment of a new organizational unit of investment. The paper presents the author remarks, conclusions and comments. This work was done within the framework of statutory research AGH No. 11.11.150.005.
Herausforderung Sri Lanka
Authors: Nagel Sven , Müller Anthea , Walter David , Hildenbrand Geza , Haas Fabian
Published: June 2014

Studenten aus Karlsruhe initiieren, planen und verwirklichen eigenverantwortlich ingenieurstechnische Entwicklungsprojekte weltweit. In diesem Bericht werden die Herausforderungen eines solchen Projektes am Beispiel der im Sommer 2013 fertiggestellten Hängebrücke im Süden Sri Lankas dargestellt. Neben der Suche nach einem passenden Projekt stellen die Finanzierung sowie die Vorbereitung des Teams auf kulturelle Eigenheiten fundamentale Aufgaben dar. Bei der Planung muss eine Konstruktion entwickelt werden, die den besonderen Beanspruchungen durch den srilankischen Dschungel dauerhaft trotzt und in einer einfachen Bauweise ohne schwere Baumaschinen und ausgebildete Fachkräfte gebaut werden kann. Um dies zu erreichen ist es erforderlich, sich in mancher Hinsicht von den im Studium gelernten Standards und Techniken zu lösen und eigene Konzepte zu entwerfen. In der knapp viermonatigen Bauphase sorgen Kommunikationsprobleme, Schwierigkeiten bei der Terminplanung und Materialbeschaffung sowie Tropenstürme für einen abwechslungsreichen Alltag auf der Baustelle. Nach dem Abschluss des Projektes zeigt sich, dass vor allem ein verlässliches Team, Durchhaltevermögen und die enge Zusammenarbeit mit den Menschen vor Ort für die erfolgreiche Umsetzung unabdingbar sind.

Challenge Sri Lanka – prospective engineers build suspension bridge in the jungle

Students from Karlsruhe University initiate, plan and develop engineering projects worldwide with sole responsibility. In summer 2013 they built a suspension bridge in a small village in the Sri Lankan jungle. This report is going to show and emphasize the challenges which come along with conducting such a project. Next to the project itself the funding needs to be discussed clearly as well as the fact that the whole team needs to be confronted with possible cultural differences and characteristics. Considering the construction of the suspension bridge it needs to be kept in mind that the material needs to be extremely solid due to the Sri Lankan humid climate. The construction of the bridge is supposed to be planned as simple as possible. University students and villagers who are not familiar with working on a construction site are going to build the bridge. In addition for logistical reasons it is not possible to bring and move big construction machines into the Sri Lankan jungle. Therefore it is necessary to throw acquired knowledge overboard and to come up with own creative concepts and ideas. The suspension bridge had been built and finished within four months. Because of communication problems, tropical storms as well as difficulties in accurate project planning and purchasing no day on the construction site was like the other. Looking back a reliable team, staying power and a close cooperation with the villagers is indispensable for completing such a tremendous project successfully.
Spannbetonbau in der DDR
Authors: Bolle Guido , Schacht Gregor , Marx Steffen
Published: June 2014

Der Beitrag gibt einen Überblick über die in der ehemaligen DDR eingesetzten Spannverfahren und stellt eines davon, das Verfahren ITB, ausführlich vor. Beim Abbruch der Brücke des 10. Jahrestages in Neubrandenburg, bei deren Errichtung dieses Spannverfahren erstmals zum Einsatz kam, wurden Material‐ und Bauteilproben entnommen und diese experimentell untersucht. Mit dem Ziel, das Schubversagen eines Spannbetonbauteils ohne schlaffe Betonstahlbewehrung zu untersuchen, wurde ein aus der Brücke herausgetrennter Träger einem Bruchversuch unterzogen, wobei verschiedene Messverfahren, wie die Photogrammetrie, die Schallemissionsanalyse und die bereichsweise Krümmungsmessung zum Einsatz kamen. Die Ergebnisse dieser experimentellen Untersuchungen werden ausführlich vorgestellt und das Tragverhalten hinsichtlich einer Versagensvorankündigung bewertet.

Investigations on a pre‐stressed concrete bridge beam without pre‐tensioned reinforcement

The paper gives an overview of the pre‐stressing systems used in the former GDR and describes one system, called ITB, in detail. During the demolition of the bridge “10. Jahrestag” in Neubrandenburg, at which this pre‐stressing system was first used, material samples and a specimen were taken and experimentally investigated. For the objective of the investigation of a pre‐stressed concrete element without non‐pre‐stressed reinforcement, a cut out beam of a bridge was loaded until failure and different measuring technologies, like the photogrammetry, the acoustic emission analyses and the sectionwise curvature‐measurement were used. The results of this experimental investigation are discussed in detail and the bearing behavior according to an unannounced failure is evaluated.
Fluorescent studies on the interaction of DNA and ternary lanthanide complexes with cinnamic acid‐phenanthroline and antibacterial activities testing
Authors: Sun Hui‐Juan , Wang Ai‐Ling , Chu Hai‐Bin , Zhao Yong‐Liang
Published: June 2014

Twelve lanthanide complexes with cinnamate (cin–) and 1,10‐phenanthroline (phen) were synthesized and characterized. Their compositions were assumed to be RE(cin)3phen (RE3+ = La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Tm3+, Yb3+, Lu3+). The interaction mode between the complexes and DNA was investigated by fluorescence quenching experiment. The results indicated the complexes could bind to DNA and the main binding mode is intercalative binding. The fluorescence quenching constants of the complexes increased from La(cin)3phen to Lu(cin)3phen. Additionally, the antibacterial activity testing showed that the complexes exhibited excellent antibacterial ability againstEscherichia coli, and the changes of antibacterial ability are in agreement with that of the fluorescence quenching constants. Copyright © 2014 John Wiley & Sons, Ltd.
Fractional factorial design to investigate stromal cell regulation of macrophage plasticity
Authors: Barminko Jeffrey A. , Nativ Nir I. , Schloss Rene , Yarmush Martin L.
Published: June 2014

Understanding the regulatory networks which control specific macrophage phenotypes is essential in identifying novel targets to correct macrophage mediated clinical disorders, often accompanied by inflammatory events. Since mesenchymal stromal cells (MSCs) have been shown to play key roles in regulating immune functions predominantly via a large number of secreted products, we used a fractional factorial approach to streamline experimental evaluation of MSC mediated inflammatory macrophage regulation. Our macrophage reprogramming metrics, human bone marrow MSC attenuation of macrophage pro‐inflammatory M1 TNFα secretion and simultaneous enhanced expression of the M2 macrophage marker, CD206, were used as analysis endpoints. Objective evaluation of a panel of MSC secreted mediators indicated that PGE2 alone was sufficient in facilitating macrophage reprogramming, while IL4 only provided partial reprogramming. Inhibiting stromal cell PGE2 secretion with Indomethacin, reversed the macrophage reprogramming effect. PGE2 reprogramming was mediated through the EP4 receptor and indirectly through the CREB signaling pathway as GSK3 specific inhibitors induced M1 macrophages to express CD206. This reprogramming pathway functioned independently from the M1 suppression pathway, as neither CREB nor GSK3 inhibition reversed PGE2 TNF‐α secretion attenuation. In conclusion, fractional factorial experimental design identified stromal derived PGE2 as the factor most important in facilitating macrophage reprogramming, albeit via two unique pathways. Biotechnol. Bioeng. 2014;111: 2239–2251. © 2014 Wiley Periodicals, Inc.
The continuum heterogeneous biofilm model with multiple limiting substrate Monod kinetics
Authors: Gonzo Elio Emilio , Wuertz Stefan , Rajal Veronica B.
Published: June 2014

We describe a novel procedure to estimate the net growth rate of biofilms on multiple substrates. The approach is based on diffusion‐reaction mass balances for chemical species in a continuum biofilm model with reaction kinetics corresponding to a Double‐Monod expression. This analytical model considers a heterogeneous biofilm with variable distributions of biofilm density, activity, and effective diffusivity as a function of depth. We present the procedure to estimate the effectiveness factor analytically and compare the outcome with values obtained by the application of a rigorous numerical computational method using several theoretical examples and a test case. A comparison of the profiles of the effectiveness factor as a function of the Thiele modulus, φ, revealed that the activity of a homogeneous biofilm could be as much as 42% higher than that of a heterogeneous biofilm, under the given conditions. The maximum relative error between numerical and estimated effectiveness factor was 2.03% at φ near 0.7 (corresponding to a normalized Thiele modulus φ* = 1). For φ < 0.3 or φ > 1.4, the relative error was less than 0.5%. A biofilm containing aerobic ammonium oxidizers was chosen as a test case to illustrate the model's capability. We assumed a continuum heterogeneous biofilm model where the effective diffusivities of oxygen and ammonium change with biofilm position. Calculations were performed for two scenarios; Case I had low dissolved oxygen (DO) concentrations and Case II had high DO concentrations, with a concentration at the biofilm–fluid interface of 10 g O2/m3. For Case II, ammonium was the limiting substrate for a biofilm surface concentration, CNs, ≤13.84 g of N/m3. At these concentrations ammonium was limiting inside the biofilm, and oxygen was fully penetrating. Conversely, for CNs > 13.84 g of N/m3, oxygen became the limiting substrate inside the biofilm and ammonium was fully penetrating. Finally, a generalized procedure to estimate the effectiveness factor for a system with multiple (n > 2) limiting substrates is given. Biotechnol. Bioeng. 2014;111: 2252–2264. © 2014 Wiley Periodicals, Inc.
The use of high pressure CO2‐facilitated pH swings to enhance in situ product recovery of butyric acid in a two‐phase partitioning bioreactor
Authors: Peterson Eric C. , Daugulis Andrew J.
Published: June 2014

Through the use of high partial pressures of CO2 (pCO2) to facilitate temporary pH reductions in two‐phase partitioning bioreactors (TPPBs), improved pH dependent partitioning of butyric acid was observed which achieved in situ product recovery (ISPR), alleviating end‐product inhibition (EPI) during the production of butyric acid by Clostridium tyrobutyricum (ATCC 25755). Through high pressure pCO2 studies, media buffering effects were shown to be substantially overcome at 60 bar pCO2, resulting in effective extraction of the organic acid by the absorptive polymer Pebax® 2533, yielding a distribution coefficient (D) of 2.4 ± 0.1 after 1 h of contact at this pressure. Importantly, it was also found that C. tyrobutyricum cultures were able to withstand 60 bar pCO2 for 1 h with no decrease in growth ability when returned to atmospheric pressure in batch reactors after several extraction cycles. A fed‐batch reactor with cyclic high pCO2 polymer extraction recovered 92 g of butyric acid to produce a total of 213 g compared to 121 g generated in a control reactor. This recovery reduced EPI in the TPPB, resulting in both higher productivity (0.65 vs. 0.33 g L−1 h−1) and yield (0.54 vs. 0.40). Fortuitously, it was also found that repeated high pCO2‐facilitated polymer extractions of butyric acid during batch growth of C. tyrobutyricum lessened the need for pH control, and reduced base requirements by approximately 50%. Thus, high pCO2‐mediated absorptive polymer extraction presents a novel method for improving process performance in butyric acid fermentation, and this technique could be applied to the bioproduction of other organic acids as well. Biotechnol. Bioeng. 2014;111: 2183–2191. © 2014 Wiley Periodicals, Inc.
Preparative crystallization of a single chain antibody using an aqueous two‐phase system
Authors: Huettmann Hauke , Berkemeyer Matthias , Buchinger Wolfgang , Jungbauer Alois
Published: June 2014

A simultaneous crystallization and aqueous two‐phase extraction of a single chain antibody was developed, demonstrating process integration. The process conditions were designed to form an aqueous two‐phase system, and to favor crystallization, using sodium sulfate and PEG‐2000. At sufficiently high concentrations of PEG, a second phase was generated in which the protein crystallization occurred simultaneously. The single chain antibody crystals were partitioned to the top, polyethylene glycol‐rich phase. The crystal nucleation took place in the sodium sulfate‐rich phase and at the phase boundary, whereas crystal growth was progressing mainly in the polyethylene glycol‐rich phase. The crystals in the polyethylene glycol‐rich phase grew to a size of >50 µm. Additionally, polyethylene glycol acted as an anti‐solvent, thus, it influenced the crystallization yield. A phase diagram with an undersaturation zone, crystallization area, and amorphous precipitation zone was established. Only small differences in polyethylene glycol concentration caused significant shifts of the crystallization yield. An increase of the polyethylene glycol content from 2% (w/v) to 4% (w/v) increased the yield from approximately 63–87%, respectively. Our results show that crystallization in aqueous two‐phase systems is an opportunity to foster process integration. Biotechnol. Bioeng. 2014;111: 2192–2199. © 2014 Wiley Periodicals, Inc.
A microgroove patterned multiwell cell culture plate for high‐throughput studies of cell alignment
Authors: Lücker Petra B. , Javaherian Sahar , Soleas John P. , Halverson Duncan , Zandstra Peter W. , McGuigan Alison P.
Published: June 2014

Grooved substrates are commonly used to guide cell alignment and produce in vitro tissues that mimic certain aspects of in vivo cellular organization. These more sophisticated tissues provide valuable in vitro models for testing drugs and for dissecting out molecular mechanisms that direct tissue organization. To increase the accessibility of these tissue models we describe a simple and yet reproducible strategy to produce 1 µm‐spaced grooved well plates suitable for conducting automated analysis of cellular responses. We characterize the alignment of four human cell types: retinal epithelial cells, umbilical vein endothelial cells, foreskin fibroblasts, and human pluripotent stem‐cell‐derived cardiac cells on grooves. We find all cells align along the grooves to differing extents at both sparse and confluent densities. To increase the sophistication of in vitro tissue organization possible, we also created hybrid substrates with controlled patterns of microgrooved and flat regions that can be identified in real‐time using optical microscopy. Using our hybrid patterned surfaces we explore: (i) the ability of neighboring cells to provide a template to organize surrounding cells that are not directly exposed to grooved topographic cues, and (ii) the distance over which this template effect can operate in confluent cell sheets. We find that in fibroblast sheets, but not epithelial sheets, cells aligned on grooves can direct alignment of neighboring cells in flat regions over a limited distance of approximately 200 μm. Our hybrid surface plate provides a novel tool for studying the collective response of groups of cells exposed to differential topographical cues. Biotechnol. Bioeng. 2014;111: 2537–2548. © 2014 Wiley Periodicals, Inc.
Study on the pharmacokinetics and metabolism of costunolide and dehydrocostus lactone in rats by HPLC‐UV and UPLC‐Q‐TOF/MS
Authors: Peng Zhangxiao , Wang Yan , Gu Xue , Guo Xiaojie , Yan Chao
Published: June 2014

A method based on high‐performance liquid chromatography coupled with ultraviolet detection was developed for studying the pharmacokinetics of costunolide (Cos) and dehydrocostus lactone (Dehy) in rats after intravenous (i.v.) administration. Following i.v. administration, the maximum plasma concentrations of Cos and Dehy were observed to be 12.29 ± 1.47 and 5.79 ± 0.13 µg/mL, respectively. The bioavailability of Cos was larger than that of Dehy; however, the clearance and the volume of distribution of Dehy were much larger than those of Cos. An ultraperformance liquid chromatography/quadrupole time‐of‐flight mass spectrometry system with automated MSE (E represents collision energy) data analysis software (MetaboLynxTM) was used to analyze and identify the metabolites of Cos and Dehy in vivo. Four metabolites of Cos and six metabolites of Dehy were discovered from the plasma, urine and feces of rats. The main metabolic pathway of Cos was phase II biotransformation, but the main metabolic pathways of Dehy was phase І biotransformation. Two sequential desaturations and N‐acetylcysteine conjugation were the common metabolic pathways of Cos and Dehy in rats. This information may be useful for the further development of the two drug candidates. Copyright © 2014 John Wiley & Sons, Ltd.
Confinement of CuII–Phthalocyanine in a Bioinspired Hybrid Nanoparticle‐Assembled Structure Yields Selective and Stable Epoxidation Catalysts
Authors: Manna Joydeb , Amali Arlin Jose , Rana Rohit Kumar
Published: June 2014

Herein, we demonstrate that a bioinspired assembly of silica nanoparticles with polyamines as structure‐directing agents similar to that known for the biosilicification of diatoms can pave the way for the efficient encapsulation of sulfonated copper–phthalocyanine in a hybrid microcapsule structure, in which the organic component provides a capable environment for its catalytic activity in epoxidation reactions and the nanoassembled structure imparts stability.
ChemInform Abstract: Structural Distortion and Band Gap Opening of Hard MnB4 in Comparison with CrB4 and FeB4.
Authors: Yang Meng , Wang Yachun , Yao Jinlei , Li Zhiping , Zhang Jian , Wu Lailei , Li Hui , Zhang Jingwu , Gou Huiyang
Published: June 2014

First‐principles calculations are presented for monoclinic MnB4 as well as orthorhombic CrB4 and FeB4.
ChemInform Abstract: Single Crystal X‐Ray Structure of Cu3TaSe4 and a Comparative Study of Cu3MX4 (M: V, Nb, Ta; X: S, Se, Te).
Authors: Ali Sk Imran , van Smaalen Sander
Published: June 2014

Single crystals of Cu3TaSe4 are obtained from a precursor that is produced by chemical vapor reaction of Cu, Ta, and Se in a molar ratio of 0.21:1.15:2 (quartz ampoule in two‐zone furnace, 1.
ChemInform Abstract: Pressure‐Induced Intersite Bi—M (M: Ru, Ir) Valence Transitions in Hexagonal Perovskites.
Authors: Ling Chris D. , et al. et al.
Published: June 2014

Pressure‐induced charge transfer from Bi to Ir/Ru in Ba3BiIr2O9, Ba3BiRu2O9, and Ba4BiIr3O12 is investigated by high‐pressure single crystal XRD, high‐pressure neutron powder diffraction, and DFT calculations.
ChemInform Abstract: Synthesis and Optical Properties of Li3Ba2La3 (MoO4)8:Sm3+ Powders for pcLEDs.
Authors: Baur Florian , Katelnikovas Arturas , Sakirzanovas Simas , Petry Ralf , Juestel Thomas
Published: June 2014

The series of Li3Ba2(La1‐xSmx)3 (MoO4)8 (0 ≤ x ≤ 1) compounds for phosphor‐converted LEDs is prepared by solid state reaction of stoichiometric amounts of Li2CO3, BaCO3, La2O3, MoO3, and Sm2O3 (porcelaine crucibles, air, 800 °C, 10 h).
ChemInform Abstract: Three Series of Quaternary Rare‐Earth Transition‐Metal Pnictides with CaAl2Si2‐Type Structures: RECuZnAs2, REAgZnP2, and REAgZnAs2.
Authors: Stoyko Stanislav S. , Ramachandran Krishna K. , Blanchard Peter E. R. , Rosmus Kimberly A. , Aitken Jennifer A. , Mar Arthur
Published: June 2014

Three series of quaternary pnictides, LnCuZnAs2 (Ln: Y, La—Nd, Sm, Gd—Lu), LnAgZnP2 (Ln: La—Nd, Sm, Gd—Dy), and LnAgZnAs2 (Ln: La—Nd, Sm, Gd—Dy) are prepared by solid reaction of the elements (evacuated silica tubes, 1.
ChemInform Abstract: Synthesis and Structural Characterization of Yttrium Polyphosphates AY(PO3)4 (A: Rb, Tl, Cs) and Site‐Selective Spectroscopy of Eu3+ Doped Samples.
Authors: Oudahmane Abdelghani , Barros Anthony , Avignant Daniel , Zambon Daniel
Published: June 2014

The new long‐chain polyphosphates MY(PO3)4 (M: Rb, Tl, Cs) are prepared by solid state reaction of stoichiometric mixtures of M2CO3, Y2O3, and NH4H2PO4 (Pt crucible, 400—450 °C, 36 h).
ChemInform Abstract: Development of Chemoselective Photoreduction of Nitro Compounds under Solar Light and Blue LED Irradiation.
Authors: Zand Zahra , Kazemi Foad , Hosseini Saber
Published: June 2014

TiO2‐P25 acts as reusable photocatalyst for the chemoselective reduction of nitroarenes.
ChemInform Abstract: Heterogeneous versus Homogeneous Copper(II) Catalysis in Enantioselective Conjugate‐Addition Reactions of Boron in Water.
Authors: Kitanosono Taku , Xu Pengyu , Kobayashi Shu
Published: June 2014

The authors compare one heterogeneous and two homogeneous copper catalyst systems for the hydroboration of unsaturated ketones followed by oxidative deboration.
ChemInform Abstract: Iron(III)triflate as a Highly Efficient, Recyclable and Green Catalyst for the N‐Boc Protection of Amines.
Authors: Feng Chengliang , Chu Ningning , Zhang Shuguang , Cai Jin , Chen Junqing , Hu Huayou , Ji Min
Published: June 2014

Various aliphatic, aromatic, and heterocyclic amines as well as aminols are selectively protected as monocarbamates in excellent yields and short reaction times.
ChemInform Abstract: An Efficient Catalyst for Ring Opening of Epoxides with Phenol and Thiophenol under Solvent‐Free Conditions.
Authors: Lu Hong‐fei , Zhou Jun‐tao , Cheng He‐long , Sun Lei‐lei , Yang Fei‐fei , Wu Run‐ze , Gao Yu‐hua , Luo Zhi‐bin
Published: June 2014

Notable advantages of the title process are solvent‐free conditions, short reaction times, simple operation, high yields, and reusability of the catalyst.
ChemInform Abstract: Synthesis of Novel Chiral Bidentate Hydroxyalkyl‐N‐heterocyclic Carbene Ligands and Their Application in Palladium‐Catalyzed Mizoroki—Heck Couplings and Asymmetric Addition of Diethylzinc to Benzaldehyde.
Authors: Faraji Laleh , Jadidi Khosrow , Notash Behrouz
Published: June 2014

The chiral hydroxyalkyl‐NHC ligand is prepared from leucine on a multi‐gram scale.
ChemInform Abstract: A One‐Pot Method Synthesis of α‐Chloroketone Dimethyl Acetals.
Authors: Zhong‐shi Zhou , Li Li , Xue‐han He
Published: June 2014

Ketones with the electron‐withdrawing groups afford the products in short times and in moderate to good yields, poor yields are observed otherwise.
ChemInform Abstract: ortho vs ipso: Site‐Selective Pd and Norbornene‐Catalyzed Arene C—H Amination Using Aryl Halides.
Authors: Dong Zhe , Dong Guangbin
Published: June 2014

This reaction provides aryl amine derivatives in good yields with high regioselectivity and shows a good functional group tolerance.
ChemInform Abstract: Unexpected Copper Mediated Benzyl O→O Migration During an Ullmann Ether Coupling.
Authors: Vanucci‐Bacque Corinne , Chaabouni Slim , Fabing Isabelle , Bedos‐Belval Florence , Baltas Michel
Published: June 2014

The title benzyl migration results in the unexpected formation of ether (IV) as the major product.
ChemInform Abstract: Iron‐Catalyzed ortho‐Allylation of Aromatic Carboxamides with Allyl Ethers.
Authors: Asako Sobi , Ilies Laurean , Nakamura Eiichi
Published: June 2014

For the first time, the iron‐catalyzed directed C—H bond activation to achieve the regioselective γ‐allylation is demonstrated.
ChemInform Abstract: Hydrocyanation of Arylidenemalonates Using Potassium Hexacyanoferrate(II) as an Eco‐Friendly Cyanide Source.
Authors: Li Zheng , Zhang Yupeng , Wen Fei , Yin Junjun , Zheng Huanhuan , Li Hongbo , Yang Jingya
Published: June 2014

The presence of two ester groups in the substrates is crucial as ethyl cinnamate (Ib) does not undergo hydrocyanation under the reaction conditions.
ChemInform Abstract: K4[Fe(CN)6] as Non‐Toxic Source of Cyanide for the Cyanation of Aryl Halides Using Pd‐β Zeolite as a Heterogeneous Catalyst.
Authors: Sajadi S. Mohammad , Maham Mehdi , Mahmoud Sarbast Ahmad
Published: June 2014

The reaction is conducted under ligand free conditions.
ChemInform Abstract: MgI2 Etherate‐Catalyzed Strecker Reaction: A Facile and Efficient Synthesis of α‐Aminonitriles from Aldimines and Trimethylsilyl Cyanide.
Authors: Lu Yongping , Wang Yanping , Zhang Xingxian
Published: June 2014

The procedure can not be applied to ketimines.
ChemInform Abstract: Palladium Nanoparticles Stabilized by Sterically Hindered Phosphonium Salts as Suzuki Cross‐Coupling Catalysts.
Authors: Ermolaev V. V. , Arkhipova D. M. , Nigmatullina L. Sh. , Rizvanov I. Kh. , Milyukov V. A. , Sinyashin O. G.
Published: June 2014

In situ generated palladium nanoparticles stabilized by a sterically hindered phosphonium salt are shown to act as an efficient catalyst for the Suzuki cross‐coupling reaction of haloarenes with arylboronic acids.
ChemInform Abstract: Oxovanadium(V)‐Induced Diastereoselective Oxidative Homocoupling of Boron Enolates.
Authors: Amaya Toru , Masuda Takaya , Maegawa Yusuke , Hirao Toshikazu
Published: June 2014

Oxovanadium(V)‐induced oxidative coupling of (Z)‐boron enolates derived from enones (I) is demonstrated to give the corresponding 2,3‐disubstituted 1,4‐diketones (II) in good yields.
ChemInform Abstract: Indium(III) Triflate‐Catalyzed [4 + 2] Benzannulation Reactions of O‐Alkynylbenzaldehydes with Enolisable Carbonyl Compounds: Selective Synthesis of Naphthyl Ketones.
Authors: Sakthivel Karuppusamy , Srinivasan Kannupal
Published: June 2014

The indium‐catalyzed benzannulation of alkynyl benzaldehydes (I) with aldehydes (II) or ketones (VI) leads to desired naphthyl ketones (III) or (VII), resp., as single products.
ChemInform Abstract: MeOTf‐Induced Carboannulation of Arylnitriles and Aromatic Alkynes: A New Metal‐Free Strategy to Construct Indenones.
Authors: Yan Xiaoyu , Zou Song , Zhao Peng , Xi Chanjuan
Published: June 2014

A variety of substituted indenones is readily prepared by a carboannulation reaction of benzonitriles with alkynes in the presence of methyl triflate.
ChemInform Abstract: A Facile Preparation of Various N‐Heterocycles Using Amides and Olefins.
Authors: Gratia Synthia S. , Vigneau Edward S. , Eltayeb Sumiea , Patel Kishan , Meyerhoefer Terence J. , Kershaw Sonia , Huang Victor , De Castro Michael
Published: June 2014

A convenient synthesis of a variety of N‐heterocycles including oxazolines, thiazolines, and dihydrodoxazines is accomplished by NIS‐promoted addition of amides or heteroanalogues amides to olefins.
ChemInform Abstract: Two‐Directional Synthesis of the Non‐Adjacent Bis(tetrahydrofuran) Core of cis‐Sylvaticin.
Authors: Quinn Kevin J. , Gage Kaylie E. , Stanners Caroline M. , Hayes Colin O. , Shanley Kathleen E. , Couvertier Shalise M.
Published: June 2014

The title core structure (I) is synthesized in seven steps and 24% overall yield from (2R,3S)‐1,2‐epoxy‐4‐penten‐3‐ol.
ChemInform Abstract: An Expedient Approach for the Synthesis of 1‐Alkyl‐4‐propionylpyrrolidin‐2‐ones
Authors: Saadi Fatma , Jebali Khaoula , Arfaoui Aicha , Amri Hassen
Published: June 2014

using a tandem addition‐cyclization reaction of primary amines with α‐functionalized propyl vinyl ketone (III)
ChemInform Abstract: α‐Amino Acid Derived Enaminones and Their Application in the Synthesis of N‐Protected Methyl 5‐Substituted‐4‐hydroxypyrrole‐3‐carboxylates and Other Heterocycles.
Authors: Groselj Uros , Zorz Mojca , Golobic Amalija , Stanovnik Branko , Svete Jurij
Published: June 2014

N‐protected α‐amino acids can be converted to enaminones [e.g. compound (III)], which can be isolated, but in many cases easily transform into 4‐hydroxypyrroles and their 4‐oxo‐tautomers [e.g. compounds (IV) and (V)].
ChemInform Abstract: Synthesis and Lipophilicity Evaluation of Some Novel Indole‐Containing Pseudopeptides.
Authors: Alavijeh Nahid S. , Ramezanpour Sorour , Alavijeh Mohammad S. , Balalaie Saeed , Rominger Frank , Misra Anil , Bijanzadeh Hamid Reza
Published: June 2014

Most of the new indole‐containing pseudopeptides (V), (VIII), and (X) possess the optimal range of lipophilicity for oral absorption, cell membrane penetration and blood‐brain barrier permeation.
ChemInform Abstract: Highly Efficient and Diastereoselective Construction of Bispirooxindoles Through a Cascade Michael‐Cyclization Reaction.
Authors: Wu Song , Zhu Xingli , He Wujun , Wang Rongming , Xie Xiaohua , Qin Dabin , Jing Linhai , Chen Zeqin
Published: June 2014

The diastereoselective synthesis of bisspirooxindoles (III) and (VI) is accomplished through a consecutive Michael addition/cyclization reaction of methyleneindolinones with 3‐isothiocyanato oxindoles in the presence of small amounts of tetramethylguanidine as the catalyst.
ChemInform Abstract: Copper‐Mediated C3‐Cyanation of Indoles by the Combination of Amine and Ammonium.
Authors: Liu Bin , Wang Jiehui , Zhang Bo , Sun Yang , Wang Lei , Chen Jianbin , Cheng Jiang
Published: June 2014

The transformation is suggested to proceed via an iminium ion, generated from TMEDA, which is sequentially attacked by indole (I) and water followed by hydrolyzation to form an intermediate aldehyde.