bluuebunny/crossref_metadata_2025 huggingface dataset:
On the possibility of viscoelastic deformation of the large south polar craters and true polar wander on the asteroid Vesta
Authors: Karimi Saman , Dombard Andrew J.
Published: September 2016

The asteroid Vesta, located within the inner asteroid belt, is a differentiated body with a prominent rotational bulge. NASA's Dawn mission revealed the presence of two large, relatively shallow impact craters in the south polar region, one with a high‐standing central peak. The shallowness and prominent central peak are reminiscent of large craters on some icy satellites that may have experienced strong topographic relaxation. The location of these basins near the south pole is also unusual and suggests true polar wander, which requires relaxation of the rotational bulge. Thus, we use the finite element method and a viscoelastic rheology to examine the feasibility of relaxation processes operating on Vesta. Given the plausible thermal state of Vesta by the decay of long‐lived radioactive elements, we find that the lithosphere is not compliant enough to allow strong relaxation of the large south polar craters, and thus the peculiar morphology is possibly a product of the formation of these large basins at a planetary scale. Additionally, the asteroid has not been warm enough to permit the relaxation of the rotational bulge. Consequently, these craters both happened to form near the south pole, as unlikely as that is.
Characterization of Thermomechanical Behavior of Ti3SiC2 and Ti2AlC Ceramics Elaborated by Spark Plasma Sintering Using Ultrasonic Means
Authors: Kozak Karolina , Dosi Ariane , Antou Guy , Pradeilles Nicolas , Chotard Thierry
Published: September 2016

In order to better understand the thermomechanical behaviors of Ti3SiC2 and Ti2AlC ceramics, sintered by spark plasma sintering process (SPS), ultrasonic pulse echography in “long bar mode” (US) and acoustic emission (AE) techniques are applied. High‐temperature investigations of the evolution of Young's modulus (E) and AE activity are carried out up to 1 473 and 1 623 K. Results show a decrease of E with increasing temperature which is more marked around maximal temperature of the thermal cycle for Ti2AlC material. Moreover, the increase of the maximal temperature of the thermal cycle influences the number of recorded cumulated hits. Both measurements (US + AE) highlight the role of the plastic deformation mechanism (motion of dislocation) activated over the brittle‐to‐plastic transition temperature.
Manipulating Cell Nanomechanics Using Micropatterns
Authors: Wang Xinlong , Hu Xiaohong , Kawazoe Naoki , Yang Yingnan , Chen Guoping
Published: September 2016

The nanomechanics of cells have been proven to play important roles in regulating cell behaviors. However, conventional measurement of cell nanomechanics that is processed on uniform surfaces lacks the control of cell morphology, which is reported to significantly influence the cell nanomechanics. This study prepares the micropatterned surfaces using photolithographic micropatterning of photoreactive poly(vinyl alcohol) on cell‐culture polystyrene plates to provide controllable and reproducible cell morphology. The nanomechanics of osteoblasts (NHOst), mesenchymal stem cells (MSCs), and osteosarcoma cell line (MG‐63) are compared on micropatterns. Cell stiffness increases with increase of spreading area due to the ordering of cytoskeleton. Disrupting F‐actin assembly reduces cell stiffness. Meanwhile, cell spreading area influences the expression of phosphoezrin that affects cell surface roughness. Rough membrane is accompanied with high non‐specific adhesion force and migration rate. The influence of spreading area on cancer cell nanomechanics is not as evident as that of normal cells indicating cancer cells behave less dependently on their microenvironment compared to normal cells. The findings of this study suggest that the nanomechanical differences between normal and cancer cells can be used as a biomarker to enhance the diagnosis of cancers. The use of micropatterns should be very useful to compare the nanomechanics of cells.
Synthesis of Optically Complex, Porous, and Anisometric Polymeric Microparticles by Templating from Liquid Crystalline Droplets
Authors: Wang Xiaoguang , Bukusoglu Emre , Miller Daniel S. , Bedolla Pantoja Marco A. , Xiang Jie , Lavrentovich Oleg D. , Abbott Nicholas L.
Published: September 2016

It is demonstrated that aqueous dispersions of micrometer‐sized liquid crystal (LC) droplets provide the basis of a general and facile methodology for the templated synthesis of spherical and nonspherical polymeric microparticles with complex internal structure and porosity. Specifically, nematic droplets of reactive (RM257)/nonreactive mesogens with distinct internal configurations are prepared using a range of approaches, the reactive mesogens are photopolymerized, and then the nonreactive mesogens are extracted to yield polymeric particles. It is found that LC droplets exhibiting bipolar, radial, axial or preradial configurations template the formation of spindle‐shaped, spherical, spherocylindrical or tear‐shaped polymeric microparticles, respectively. Each type of microparticle exhibits distinct optical signatures indicating the presence of an internal LC‐templated, anisotropic polymer network. In addition, by using a microfluidic system to generate monodisperse LC droplets containing 10%–40% wt/wt of RM257, spindle‐shaped microparticles with tailored aspect ratios ranging from 2.4 to 1.2 are formed. The mass density of spherical microparticles templated from radial LC droplets can be tuned to range from 0.2 to 0.6 g cm−3, revealing the introduction of porosity (confirmed by electron microscopy) with a volume‐average pore diameter of 39 ± 16 nm (obtained from nitrogen sorption isotherms).
Triboelectric and Piezoelectric Effects in a Combined Tribo‐Piezoelectric Nanogenerator Based on an Interfacial ZnO Nanostructure
Authors: Yang Xiya , Daoud Walid A.
Published: September 2016

In this contribution, combined triboelectric and piezoelectric generators (TPEG) with a sandwich structure of aluminum‐polydimethylsiloxane/polyvinylidene fluoride composite‐carbon (Al‐PPCF‐Carbon) are fabricated for the purpose of mechanical energy harvesting. Improved by the surface modification of PPCF with zinc oxide (ZnO) nanorods through a hydrothermal method, the TPEG generates an open‐circuit voltage (Voc) of ≈40 V, a short‐circuit current (Isc) of 0.28 μA with maximum power density of ≈70 mWm−2, and maximum conversion efficiency of 34.56%. Subsequently, in order to understand the transduction mechanism of the triboelectric and piezoelectric effects, analyses focusing on the potential composition ratio in the final output and the impact of ZnO interfacial nanostructure are carried out. The observed potential ratio between triboelectric and piezoelectric effects is 12.75:1 and the highest potential improvement by ZnO nanorods of 21.8 V is achieved by the TPEG fabricated with spacer. Finally, the relationships between the voltage, power density, conversion efficiency, and the external load resistances are also discussed. Overall, the fabricated TPEG is proved to be a simple and effective nanogenerator in mechanical energy conversion with enhanced output potential and conversion efficiency.
Unleashing Strain Induced Ferroelectricity in Complex Oxide Thin Films via Precise Stoichiometry Control
Authors: Haislmaier Ryan C. , Grimley Everett D. , Biegalski Michael D. , LeBeau James M. , Trolier‐McKinstry Susan , Gopalan Venkatraman , Engel‐Herbert Roman
Published: September 2016

Strain tuning has emerged as a powerful means to enhance properties and to induce otherwise unattainable phenomena in complex oxide films. However, by employing strain alone, the predicted properties sometimes fail to emerge. In this work, the critical role of precise stoichiometry control for realizing strain‐induced ferroelectricity in CaTiO3 films is demonstrated. An adsorption controlled growth window is discovered for CaTiO3 films grown by hybrid molecular beam epitaxy, which ensures an excellent control over the Ti:Ca atomic percent ratio of <0.8% in the films. Superior ferroelectric and dielectric properties are found for films grown inside the stoichiometric growth window, yielding maximum polarization, dielectric constant, and paraelectric‐to‐ferroelectric transition temperatures. Outside this growth window, properties are severely deteriorated and ultimately suppressed by defects in the films. This study exemplifies the important role of precise compositional control for achieving strain‐induced properties. Untangling the effects of strain and stoichiometry on functional properties will accelerate both fundamental discoveries yet to be made in the vast materials design space of strained complex oxide films, as well as utilization of strain‐stabilized phenomena in future devices.
Multifunctional Photonics Nanoparticles for Crossing the Blood–Brain Barrier and Effecting Optically Trackable Brain Theranostics
Authors: Singh Ajay , Kim Woong , Kim Youngsun , Jeong Keunsoo , Kang Chi Soo , Kim YoungSoo , Koh Joonseok , Mahajan Supriya D. , Prasad Paras N. , Kim Sehoon
Published: September 2016

Theranostic photonic nanoparticles (TPNs) that cross the blood–brain barrier (BBB) and efficiently deliver a therapeutic agent to treat brain diseases, simultaneously providing optical tracking of drug delivery and release, are introduced. These TPNs are constructed by physical encapsulation of visible and/or near‐infrared photonic molecules, in an ultrasmall micellar structure (<15 nm). Phytochemical curcumin is employed as a therapeutic as well as visible‐emitting photonic component. In vitro BBB model studies and animal imaging, as well as ex vivo examination, reveal that these TPNs are capable of transmigration across the BBB and subsequent accumulation near the orthotopic xenograft of glioblastoma multiforme (GBM) that is the most common and aggressive brain tumor whose vasculature retains permeability‐resistant properties. The intracranial delivery and release of curcumin can be visualized by imaging fluorescence produced by energy transfer from curcumin as the donor to the near‐infrared emitting dye, coloaded in TPN, where curcumin induced apoptosis of glioma cells. At an extremely low dose of TPN, a significant therapeutic outcome against GBM is demonstrated noninvasively by bioluminescence monitoring of time‐lapse proliferation of luciferase‐expressing U‐87 MG human GBM in the brain. This approach of TPN can be generally applied to a broad range of brain diseases.
Hemoglobin‐Conjugated Gelatin Microsphere as a Smart Oxygen Releasing Biomaterial
Authors: Paciello Antonio , Amalfitano Giuseppe , Garziano Alessandro , Urciuolo Francesco , Netti Paolo A.
Published: September 2016

In this study, a novel micrometric biomaterial acting as a cyclic oxygen releasing system is designed. Human hemoglobin (Hb) is conjugated to the surface of gelatin microspheres (GM) to produce gelatin hemoglobin oxygen depot (G‐HbOD). G‐HbOD is obtained by means of two different conjugation strategies. The degree of conjugation of GM surfaces in terms of free amino groups by using HPLC is first evaluated. By following the strategy A (G‐HbOD_A), Hb is conjugated to GM by means of the formation of a polyurethane linker. In the strategy B (G‐HbOD_B) the conjugation occurs via amide bound formation. Physical and morphological differences between G‐HbOD_A and G‐HbOD_B are investigated by means of Fourier Transform Infrared Spectroscopy (FTIR), Inductively Coupled Plasma Optical Emission Spectroscopy (ICP‐OES), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Differences in oxygen uptake/release kinetics are found depending on the conjugation strategy and it is proved that G‐HbOD works under repeated cycles in microfluidic chip. Moreover, G‐HbOD is also able to work as oxygen depot in the early stages of 3D cell cultures.
Acetalated Dextran Microparticulate Vaccine Formulated via Coaxial Electrospray Preserves Toxin Neutralization and Enhances Murine Survival Following Inhalational Bacillus Anthracis Exposure
Authors: Gallovic Matthew D. , Schully Kevin L. , Bell Matthew G. , Elberson Margaret A. , Palmer John R. , Darko Christian A. , Bachelder Eric M. , Wyslouzil Barbara E. , Keane‐Myers Andrea M. , Ainslie Kristy M.
Published: September 2016

Subunit formulations are regarded as the safest type of vaccine, but they often contain a protein‐based antigen that can result in significant challenges, such as preserving antigenicity during formulation and administration. Many studies have demonstrated that encapsulation of protein antigens in polymeric microparticles (MPs) via emulsion techniques results in total IgG antibody titers comparable to alum formulations, however, the antibodies themselves are non‐neutralizing. To address this issue, a coaxial electrohydrodynamic spraying (electrospray) technique is used to formulate a microparticulate‐based subunit anthrax vaccine under conditions that minimize recombinant protective antigen (rPA) exposure to harsh solvents and high shear stress. rPA and the adjuvant resiquimod are encapsulated either in separate or the same acetalated dextran MPs. Using a murine model, the electrospray formulations lead to higher IgG2a subtype titers as well as comparable total IgG antibody titers and toxin neutralization relative to the FDA‐approved vaccine (BioThrax). BioThrax provides no protection against a lethal inhalational challenge of the highly virulent Ames Bacillus anthracis anthrax strain, whereas 50% of the mice vaccinated with separately encapsulated electrospray MPs survive. Overall, this study demonstrates the potential use of electrospray for encapsulating protein antigens in polymeric MPs.
PHB‐Based Gels as Delivery Agents of Chemotherapeutics for the Effective Shrinkage of Tumors
Authors: Wu Yun‐Long , Wang Han , Qiu Ying‐Kun , Liow Sing Shy , Li Zibiao , Loh Xian Jun
Published: September 2016

Injectable thermogel to deliver chemotherapeutics in a minimally invasive manner and to achieve their long term sustained release at tumor sites to minimize side effects is attractive for chemotherapy and precision medicine, but its rational design remains a challenge. In this work, a copolymer with natural biodegradable poly[(R)‐3‐hydroxybutyrate] (PHB), hydrophilic poly(ethylene glycol), and temperature sensitive poly(propylene glycol) blocks linked by urethane linkages is designed to show thermogelling characteristics which are beneficial for minimally invasive injection and safe degradation. This thermogelling polymer possesses in vitro biocompatibility with very low cyto‐toxicity in HEK293 cells. Furthermore, it is able to form the gel to achieve the controllable release of paclitaxel (PTX) and doxorubicin (DOX) by adjusting polymer concentrations. A rodent model of hepatocarcinoma has been performed to demonstrate the in vivo applications of this PHB‐based thermogel. The drug‐loaded thermogel has been intratumorally injected and both PTX‐loaded and DOX‐loaded thermogel have significantly slowed down tumor growth. This work represents the first time that injectable PHB thermogels have possessed good controllable release effect of chemotherapeutics against the in vivo model of tumors and will benefit various applications, including on‐demand drug delivery and personalized medicine.
Biomimicking Platelet–Monocyte Interactions as a Novel Targeting Strategy for Heart Healing
Authors: Cheng Bill , Toh Elsie K. W. , Chen Kun‐Hung , Chang Yuan‐Chih , Hu Che‐Ming J. , Wu Han‐Chung , Chau Lee‐Young , Chen Peilin , Hsieh Patrick C. H.
Published: September 2016

In patients who survive myocardial infarction, many go on to develop congestive heart failure (CHF). Despite ongoing efforts to develop new approaches for postinfarction therapy, there are still no effective therapeutic options available to CHF patients. Currently, the delivery of cardioprotective drugs relies entirely on passive uptake via the enhanced permeability and retention (EPR) effect which occurs in proximity to the infarction site. However, in ischemic disease, unlike in cancer, the EPR effect only exists for a short duration postinfarction and thus insufficient for meaningful cardioprotection. Splenic monocytes are recruited to the heart in large numbers postinfarction, and are known to interact with platelets during circulation. Therefore, the strategy is to exploit this interaction by developing platelet‐like proteoliposomes (PLPs), biomimicking platelet interactions with circulating monocytes. PLPs show strong binding affinity for monocytes but not for endothelial cells in vitro, mimicking normal platelet activity. Furthermore, intravital multiphoton imaging shows that comparing to plain liposomes, PLPs do not aggregate on uninjured endothelium but do accumulate at the injury site 72 h postinfarction. Importantly, PLPs enhance the targeting of anti‐inflammatory drug, cobalt protoporphyrin, to the heart in an EPR‐independent manner, which result in better therapeutic outcome.
Silica‐Coated Nonstoichiometric Nano Zn‐Ferrites for Magnetic Resonance Imaging and Hyperthermia Treatment
Authors: Starsich Fabian H. L. , Sotiriou Georgios A. , Wurnig Moritz C. , Eberhardt Christian , Hirt Ann M. , Boss Andreas , Pratsinis Sotiris E.
Published: September 2016

Large‐scale and reproducible synthesis of nanomaterials is highly sought out for successful translation into clinics. Flame aerosol technology with its proven capacity to manufacture high purity materials (e.g., light guides) up to kg h−1 is explored here for the preparation of highly magnetic, nonstoichiometric Zn‐ferrite (Zn0.4Fe2.6O4) nanoparticles coated in situ with a nanothin SiO2 layer. The focus is on their suitability as magnetic multifunctional theranostic agents analyzing their T2 contrast enhancing capability for magnetic resonance imaging (MRI) and their magnetic hyperthermia performance. The primary particle size is closely controlled from 5 to 35 nm evaluating its impact on magnetic properties, MRI relaxivity, and magnetic heating performance. Most importantly, the addition of Zn in the flame precursor solution facilitates the growth of spinel Zn‐ferrite crystals that exhibit superior magnetic properties over iron oxides typically made in flames. These properties result in strong MRI T2 contrast agents as shown on a 4.7 T small animal MRI scanner and lead to a more efficient heating with alternating magnetic fields. Also, by injecting Zn0.4Fe2.6O4 nanoparticle suspensions into pork tissue, MR‐images are acquired at clinically relevant concentrations. Furthermore, the nanothin SiO2 shell facilitates functionalization with polymers, which improves the biocompatibility of the theranostic system.
Meters‐Long Flexible CoNiO2‐Nanowires@Carbon‐Fibers Based Wire‐Supercapacitors for Wearable Electronics
Authors: Ai Yuanfei , Lou Zheng , Li La , Chen Shuai , Park Ho Seok , Wang Zhiming M. , Shen Guozhen
Published: September 2016

Wire‐supercapacitors have drawn extensive attentions as a promising candidate for future wearable electronic devices. However, the relative lower energy densities and imperfect physical properties (e.g., length, tenacity, flexibility, and stability) seriously hinder their real applications as energy storage devices in wearable electronics. Herein, the fabrication of wire‐supercapacitors is reported with the length of longer than 1 m, based on CoNiO2‐nanowires@carbon‐fibers electrodes with a high capacity of 1.68 mF cm−1 and a high energy density of 0.95 mWh cm−3, respectively. The device shows no obvious performance degradation when suffering cycling, bending, pulling, tying, and weaving. After weaving as Chinese knot, watchband, belt, and clothes textile, the wire‐supercapacitors work well as the wearable energy‐storage units to power the personal electronics.
Kinetics of homogeneous 5‐hydroxymethylfurfural oxidation to 2,5‐furandicarboxylic acid with Co/Mn/Br catalyst
Authors: Zuo Xiaobin , Chaudhari Amit S. , Snavely Kirk , Niu Fenghui , Zhu Hongda , Martin Kevin J. , Subramaniam Bala
Published: September 2016

2,5‐furandicarboxylic acid (FDCA) is a potential non‐phthalate based bio‐renewable substitute for terephthalic acid‐based plastics. Herein, we present an investigation of the oxidation rate of 5‐hydroxymethylfurfural (HMF) to FDCA in acetic acid medium using Co/Mn/Br catalyst. Transient concentration profiles of the reactant (HMF), intermediates [2,5‐diformylfuran (DFF), 5‐formyl‐2‐furancarboxylic acid (FFCA)], and the desired product (FDCA) were obtained for this relatively fast reaction in a stirred semi‐batch reactor using rapid in‐line sampling. Comparison of the effective rate constants for the series oxidation steps with predicted gas–liquid mass transfer coefficients reveals that except for the FFCA → FDCA step, the first two oxidation steps are subject to gas–liquid mass transfer limitations even at high stirrer speeds. Novel reactor configurations, such as a reactor in which the reaction mixture is dispersed as fine droplets into a gas phase containing oxygen, are required to overcome oxygen starvation in the liquid phase and further intensify FDCA production. © 2016 American Institute of Chemical Engineers AIChE J, 63: 162–171, 2017
Catalytic Cycloisomerization–Fluorination Sequence of N‐Propargyl Amides by Iodoarene/HF⋅Pyridine/Selectfluor Systems
Authors: Asari Naoki , Takemoto Yusuke , Shinomoto Yukino , Yagyu Takuma , Yoshimura Akira , Zhdankin Viktor V. , Saito Akio
Published: September 2016

As a first example of metal‐free and catalytic fluorinative transformations of alkynes, we developed a cycloisomerization–fluorination sequence of N‐propargyl amides catalyzed by an iodine(III) species. The iodine(III) catalyst is in situ generated from iodoarene as a precatalyst with Selectfluor as a fluorinating oxidant in the presence of HF⋅pyridine.
Delayed massive epistaxis from traumatic intracranial aneurysm after blunt facial injury
Authors: Nakamura Hajime , Fujinaka Toshiyuki , Tasaki Osamu , Yoshimine Toshiki
Published: September 2016

Cases

Traumatic intracranial aneurysm following blunt head injury is uncommon but can be induced by extension of skull base fracture and causes unexpected hemorrhagic complications. We present two cases of traumatic intracranial aneurysm in the paraclinoid area that was revealed by delayed massive epistaxis. Lack of initial neurological deficits omitted screening for cerebrovascular injury.

Outcome

Internal trapping was carried out using endovascular techniques in both cases, with extracranial–intracranial bypass in one case. No recurrent bleeding occurred in either case.

Conclusion

To prevent unexpected delayed life‐threatening hemorrhagic accidents, careful assessment of skull‐base fracture is prerequisite, even in cases of mild facial injury.
Tandem Ring‐Opening–Ring‐Closing Metathesis for Functional Metathesis Catalysts
Authors: Nagarkar Amit A. , Yasir Mohammad , Crochet Aurelien , Fromm Katharina M. , Kilbinger Andreas F. M.
Published: September 2016

Use of a tandem ring‐opening–ring‐closing metathesis (RORCM) strategy for the synthesis of functional metathesis catalysts is reported. Ring opening of 7‐substituted norbornenes and subsequent ring‐closing metathesis forming a thermodynamically stable 6‐membered ring lead to a very efficient synthesis of new catalysts from commercially available Grubbs’ catalysts. Hydroxy functionalized Grubbs’ first‐ as well as third‐generation catalysts have been synthesized. Mechanistic studies have been performed to elucidate the order of attack of the olefinic bonds. This strategy was also used to synthesize the ruthenium methylidene complex.
Hochgenaue Berechnung der Kohäsionsenergie von festem Argon mit Abweichungen im J/mol‐Bereich
Authors: Schwerdtfeger Peter , Tonner Ralf , Moyano Gloria E. , Pahl Elke
Published: September 2016

Wir präsentieren Rechnungen der Kohäsionsenergie von Argon in der kubisch und hexagonal dichtesten Kugelpackung mit einer noch nie zuvor erreichten Genauigkeit im Bereich von 5 J mol−1 (dies entspricht 0.05 % der gesamten Kohäsionsenergie). Dieselbe relative Genauigkeit im Vergleich zu experimentellen Daten wurde auch für die Gitterkonstante des flächenzentrierten Gitters mit einer absoluten Abweichung von ungefähr 0.003 Å erreicht. Die hohe Genauigkeit wurde durch die Verwendung von wellenfunktionsbasierten Methoden im Rahmen einer Mehrkörperentwicklung der Wechselwirkungsenergie ermöglicht. Statische Beiträge der Zwei‐, Drei‐ und Vierkörperfragmente des Kristalls, die jeweils mit einer Genauigkeit von unter 1 J mol−1 berechnet wurden, wurden durch harmonische und anharmonische Nullpunktschwingungskorrekturen ergänzt. Für Edelgas‐Festkörper erreicht die Computerchemie hiermit experimentelle Genauigkeit oder übertrifft diese sogar.
Stereo‐ and Regioselective Alkyne Hydrometallation with Gold(III) Hydrides
Authors: Pintus Anna , Rocchigiani Luca , Fernandez‐Cestau Julio , Budzelaar Peter H. M. , Bochmann Manfred
Published: September 2016

The hydroauration of internal and terminal alkynes by gold(III) hydride complexes [(C^N^C)AuH] was found to be mediated by radicals and proceeds by an unexpected binuclear outer‐sphere mechanism to cleanly form trans‐insertion products. Radical precursors such as azobisisobutyronitrile lead to a drastic rate enhancement. DFT calculations support the proposed radical mechanism, with very low activation barriers, and rule out mononuclear mechanistic alternatives. These alkyne hydroaurations are highly regio‐ and stereospecific for the formation of Z‐vinyl isomers, with Z/E ratios of >99:1 in most cases.
Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)–Superoxo and Manganese(IV)–Peroxo Complexes
Authors: Hong Seungwoo , Kumar Pankaj , Cho Kyung‐Bin , Lee Yong‐Min , Karlin Kenneth D. , Nam Wonwoo
Published: September 2016

Reactions of nonheme FeIII–superoxo and MnIV–peroxo complexes bearing a common tetraamido macrocyclic ligand (TAML), namely [(TAML)FeIII(O2)]2− and [(TAML)MnIV(O2)]2−, with nitric oxide (NO) afford the FeIII–NO3 complex [(TAML)FeIII(NO3)]2− and the MnV–oxo complex [(TAML)MnV(O)]− plus NO2−, respectively. Mechanistic studies, including density functional theory (DFT) calculations, reveal that MIII–peroxynitrite (M=Fe and Mn) species, generated in the reactions of [(TAML)FeIII(O2)]2− and [(TAML)MnIV(O2)]2− with NO, are converted into MIV(O) and .NO2 species through O−O bond homolysis of the peroxynitrite ligand. Then, a rebound of FeIV(O) with .NO2 affords [(TAML)FeIII(NO3)]2−, whereas electron transfer from MnIV(O) to .NO2 yields [(TAML)MnV(O)]− plus NO2−.
Rotationally Active Ligands: Dialing‐Up the Co‐conformations of a [2]Rotaxane for Metal Ion Binding
Authors: Baggi Giorgio , Loeb Stephen J.
Published: September 2016

A novel [2]rotaxane was constructed that has a bidentate N,N′‐chelate as part of a rigid, H‐shaped axle and a 24‐membered crown ether macrocycle containing six ether O‐atoms and an olefinic group as the wheel. This unique topology produces a ligand with the ability to dial‐up different donor sets for complexation to metal ions by simply rotating the wheel about the axle. The solution and solid‐state structures of the free ligand and complexes with Li+ and Cu+ show how the ligand adopts different rotational co‐conformations for each. The Li+ ion uses the N,N′‐chelate and O‐donors while the Cu+ center is coordinated to both O‐donors and the olefinic group. This concept of rotationally active ligands should be possible with a wide variety of donor sets and could find broad application in areas of coordination chemistry, such as catalysis and metal sequestration.
Synthesis, structures, and density functional theory computational study of thiophene‐containing and fluorodecorated imine‐linked polymers
Authors: Altarawneh Suha S. , Jazzazi Taghreed M. A. , Ababneh Taher S. , Al Shboul Tareq M. A. , Al Jaafreh Ibtesam Y.
Published: September 2016

A new series of extended–conjugated and thermally stable thiophene‐containing imine‐linked polymers were synthesized via a Schiff‐base condensation reaction between aryl aldehydes and 2,6‐diaminopyridine building blocks. The backbones of the polymers were functionalized with phenyl, fluorosubstituted phenyl, thienyl, and pyridyl aromatic rings. The successful synthesis was confirmed with spectrochemical characterization techniques, including IR, 1H‐NMR, 13C‐NMR, and elemental analyses. The electronic properties of the polymers were investigated with ultraviolet–visible (UV–vis) absorption spectroscopy; the properties were collected experimentally and calculated with density functional theory (DFT) in the gas phase. The maximum absorption calculated from DFT was higher than the experimental values by about 60 nm; this was attributed to the absence of the solvent effect in the DFT case. The frontier molecular orbital ((HOMO) highest occupied molecular orbital and (LUMO) lowest unoccupied molecular orbital), optical band gap (Eg), and total energy (ET) values of the optimized structures were calculated. Apparently, there was a significant relation between the number of thiophene rings and the resulting Eg and ET values. As the number of thiophene rings in the polymer chain increased, Eg and ET decreased, and the thermal stability of the polymers increased. Eg and the absorption band edges were determined experimentally from the UV–vis and transmittance spectra, respectively. Poly(terthienyl–azomethine–pyridine–azomethine), with the highest thiophene content, had the lowest experimental and calculated Eg values (2.10 and 2.63 eV, respectively). In contrast, upon fluorination, poly[(2,5‐dithienyl–1,4‐difluorobenzene)–azomethine–pyridine–azomethine] exhibited the highest Eg (2.81 eV) and absorption band edges (2.94 eV), whereas the thermal stability decreased to 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44331.
Production and characterization of films containing poly(hydroxybutyrate) (PHB) blended with esterified alginate (ALG‐e) and poly(ethylene glycol) (PEG)
Authors: Ribeiro Lopes Jamilly , Azevedo dos Reis Rodrigo , Almeida Luís Eduardo
Published: September 2016

Alternative materials have long been studied and developed to replace conventional skin dressings with the emergence of new biopolymers and development of polymeric film fabrication techniques. As a new material for polymeric dressings, films of poly(hydroxybutyrate) (PHB) blended with esterified alginate (ALG‐e) and poly(ethyleneglycol) was studied. The esterification of sodium alginate (ALG‐e) generated a material with some amphiphilic characteristics and increased compatibility with the PHB. PEG was added as plasticizer in PHB/ALG‐e films was also tested, since PEG is often used in blends with PHB to improve flexibility and reduce hydrophobicity. At the amounts studied, it was found that both PEG and ALG‐e increase the degree of crystallinity, but a decrease was observed in the hydrophobic nature of PHB films. At the maximum concentration of ALG‐e and PEG used an increase in water vapor permeability and a decrease in tensile strength was reached due to the synergistic effect caused by better homogenization of PEG and ALG‐e in the PHB matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44362.
Imperilled species in aquatic ecosystems: emerging threats, management and future prognoses
Authors: Gangloff Michael M. , Edgar Graham J. , Wilson Ben
Published: September 2016

Earth's aquatic habitats are some of its most important ecosystems and support populations of many of its most imperilled species. The future demands of Earth's growing human populations will increasingly stress its aquatic resources on multiple spatial and temporal scales, as highlighted by numerous authors when predicting trends in biodiversity in many key aquatic hotspots.

Identifying key stressors and understanding potential linkages between these stressors are important first steps to mitigating human impacts on at‐risk aquatic resources. Here, an overview is provided of the established and emerging threats to aquatic biodiversity at local, regional and global scales, including emerging diseases, expanding influence of invasive species, new industries, and the accelerating trajectory of climate change, as well as perspectives on potential management strategies.

Copyright © 2016 John Wiley & Sons, Ltd.
Connecting the shifting currents of aquatic science and policy
Authors: Ormerod S. J. , Ray G. Carleton
Published: September 2016

The interface between science and policy is often contentious and characterized by mutual suspicion, yet is critical to both halves of the divide. The application of science to real‐world problems is ultimately one of the greatest markers of scientific achievement, while policy‐makers can reduce the risks of failure by drawing on good evidence. The disproportionately large resource value of inland waters and marine systems together make synergies between science and policy particularly pertinent.

Aquatic science has shaped major policy or regulatory legislation, with examples such as the US Clean Water Act (1972) and EU Water Framework Directive (2000/60/EC) deeply rooted in evidence. Modern policy examples are also emerging that can respond to the need for resilience to global change, the protection of natural capital and the sustainable management of ecosystem services. However, practical applications so far remain rudimentary.

There have been extensive uses of aquatic conservation science to evaluate the outcomes from past policy implementation. Examples are the role of the EU Large Combustion Plants Directive (88/609/EEC), EU Urban Wastewater Treatment Directive (91/271/EEC) and the US Clean Water Act (1972) in restoring polluted, acidified, and urbanized fresh waters. However, larger‐scale and longer‐term data are required to reveal such policy effects more fully. Evaluations of policies to address recent problems in marine waters affected by climate change, acidification, or anoxia are far less complete.

The authors suggest that aquatic scientists can play a pivotal role in identifying gaps or failings in policy or regulatory practice, and we urge our colleagues in aquatic conservation to recognize this role with conviction. A specific policy need is identified – to recognize more fully the importance of connectivity among land, inland waters, and seas to avoid high environmental costs, to capture conservation benefits, and to build resilience in aquatic ecosystems as, arguably, the world's most important environments.

Copyright © 2016 John Wiley & Sons, Ltd.
Revisiting the Vomeronasal System From an Integrated Perspective
Authors: Salazar Ignacio , Barrios Arthur W. , SáNchez‐Quinteiro Pablo
Published: September 2016

“Olfactory subsystems” is a relatively new terminology to refer to the different regions of the nasal cavity featuring olfactory sensory neurons. In mice, the olfactory chemical cues are detected in four well delimited areas: the main olfactory epithelium, the septal organ, Grüneberg's ganglion, and the sensory epithelium of the vomeronasal organ. Nevertheless, such distribution is by no means exhibited by all mammals. In microsmatic mammals –humans included– the only existing olfactory subsystem is the main olfactory epithelium. This raises the question of whether the lack of certain olfactory structures in those species implies that they are unable to identify certain olfactory signals, or on the contrary, their main olfactory epithelium assumes such role. It would be interesting to determine, in the context of biomedical research, if the sense of smell in humans is fully or partially endowed with the wide range of functions assigned to the vomeronasal system in mice. If it is not, presumptive implications of the lack of such functions should be addressed in human health and well‐being. Anat Rec, 299:1488–1491, 2016. © 2016 Wiley Periodicals, Inc.
Landing Auto‐Pilots for Aircraft Motion in Longitudinal Plane using Adaptive Control Laws Based on Neural Networks and Dynamic Inversion
Authors: Lungu Mihai , Lungu Romulus
Published: September 2016

This paper presents two new automatic landing systems (ALSs) for aircraft motion in longitudinal plane; the model of the landing geometry determines the flight trajectory and the aircraft calculated altitude; the flight trajectory during landing consists of two parts: the glide slope and the flare. Both designed ALSs have an adaptive system (ACS) for the aircraft output's control; for the first ALS, the output vector consists of the flying altitude and the longitudinal velocity, while, for the second ALS, the output variables are the pitch angle and the longitudinal velocity of aircraft. The second variant of ALS also contains an altitude controller providing the calculated pitch angle. The calculated altitude (for the first ALS), the calculated pitch angle (for the second ALS), and the desired flight velocity are provided to the ACS by means of a block consisting of two reference models. ACS is based on the dynamic inversion concept and contains an adaptive controller which includes a linear dynamic compensator, a state observer, a neural network, and a Pseudo Control Hedging block. The paper is focused both on the design of the two ALSs and on their complex software implementation and validation.
Verbundverhalten von Vollgewindeschrauben in Brettschichtholzbauteilen
Authors: Ayoubi Mazen
Published: September 2016

Zur Beschreibung des Verbundverhaltens und der Kraftübertragung von selbstbohrenden Vollgewindeschrauben bei großen Verbund‐ und Einbindelängen in Brettschichtholzbauteilen wurden experimentelle, analytische und numerische Untersuchungen am Lehrstuhl für Tragkonstruktionen der RWTH Aachen in Zusammenarbeit mit dem Institut für Bauforschung (ibac) der RWTH Aachen durchgeführt. Die experimentellen Untersuchungen umfassen mehr als 160 Pull‐Out‐Versuche sowie 84 Lasteinleitungsversuche, darüber hinaus Versuche zum Einfluss eines Längsrisses sowie einer eingebetteten Schraubenspitze auf das Verbundtragverhalten. Die parallel durchgeführten numerischen und analytischen Untersuchungen bilden die Basis zur Erstellung von Modellen zur Beschreibung des Tragverhaltens und der Kraftübertragung zwischen Schraube und Holz. Die gewonnenen Erkenntnisse ermöglichen die Bestimmung eines Bemessungsansatzes unter besonderer Berücksichtigung der Anisotropie des Holzes. In diesem Beitrag werden die Untersuchungsergebnisse, die im Rahmen des von der Deutschen Forschungsgemeinschaft (DFG) geförderten Projekts [1] ermittelt wurden, dargestellt. Teil 1 behandelt die experimentellen Untersuchungen [2], Teil 2 die analytischen und numerischen Betrachtungen sowie die Herleitung eines Verbundmodells zur Berechnung der Verankerungslänge.
Genauigkeit. Zur Ausbildung einer epistemischen Tugend im ,langen 19. Jahrhundert‘
Authors: Krajewski Markus
Published: September 2016

Exactitude. The Genesis of an Epistemic Virtue in the ‘Long Nineteenth Century’. The article examines the genesis of exactitude as an epistemic virtue in both scholarly and scientific contexts in the 19th century, mainly in Prussia. Starting with an influential historiographic work on ancient metrology three semantic fields of accuracy, exactitude and precision are differentiated and pursued in their etymologies as well as applications. The historic situation between 1790 and 1860 is identified as the crucial period when the exactness of the exact sciences as well as the notion of accuracy in the humanities start to diverge from one another in order to develop an epistemic virtue each on its own.
Die Neuordnung pflanzengeografischen Wissens als „Transitzone“ Wallacea. Ein amerikanisches Expansionsprojekt auf den Philippinen, 1902–1928
Authors: Walch Sonja
Published: September 2016

The Reshaping of Phytogeographical Knowledge as the “Transition zone” Wallacea: An American Expansion Project in the Philippines, 1902–1928. This paper examines the development of a concept that to this day plays an important role in biogeography: the region Wallacea. Focussing on the work of the American tropical botanist Elmer D. Merrill in the Philippines, I argue that his research on the geographical movement and settlement of Philippine plants reflects a shift in the United States’ scientific and cultural understanding of the Pacific area towards a notion of “American tropics”. While inventorying plants for the American administration from 1901 to 1923, the composition of Philippine flora prompted Merrill to question biogeographical regionalization in Wallace's Malay Archipelago. Not being able to situate the Philippine flora within “Asian” or “Australasian” biota, Merrill described the islands as an area of trans‐regional plant migration. Together with the paleontologist Roy E. Dickerson, he later conceptualized the region Wallacea as biogeographical “transition zone” between the Philippines and Australia. In addition to the scientific conceptualization, Wallacea constitutes a space between two biogeographical subregions, whose flora was considered as being part of both, but could not be unambiguously attributed to either of these regions. In this respect, the plants resembled the inhabitants of the United States’ insular overseas territories, who were legally defined neither as aliens nor as citizens. In this sense, Wallacea embodies epistemic as well as geopolitical boundaries, while its case also illustrates some of the ways in which colonial interests in the usability of plants found expression in botanical research during the early period of American overseas expansion.
Misinterpreted Documents and Ignored Physical Facts: The History of ‘Hitler's Atomic Bomb’ needs to be corrected
Authors: Popp Manfred
Published: September 2016

Zusammenfassung: Fehlinterpretierte Dokumente und ignorierte physikalische Fakten: Die Geschichte von ,Hitlers Atombombe‘ muss korrigiert werden. Warum haben die deutschen Physiker während des Zweiten Weltkriegs keine Atombombe entwickelt? Seit mehr als 25 Jahren sind sich die Historiker einig, dass die deutschen Physiker wussten, wie eine Atombombe gebaut werden muss, dass aber ein Programm wie das amerikanische Manhattan‐Projekt zu ihrer Realisierung in Deutschland, erst recht während des Krieges, unmöglich war. Eine genaue Analyse aller erhaltenen Original‐Dokumente über die Arbeit an der Atombombe während des ,Dritten Reichs‘ zeigt jedoch erhebliche Fehler der Autoren durch unvollständige Analyse der Dokumente, falsches Verständnis naturwissenschaftlicher Erläuterungen und Ignorieren physikalischer Fakten. Es wird nachgewiesen, dass die deutschen Physiker bis zum Ende des Krieges nicht bemerkt hatten, dass eine Atombombe nur mit schnellen Neutronen realisiert werden kann. Nur Heisenberg hatte das richtige Prinzip spät erkannt, es aber nicht eindeutig kommuniziert und auch in keiner Weise physikalisch vertieft. Die physikalisch korrekte Interpretation der Dokumente zeigt, dass die deutschen Physiker während des Krieges erfolglos versuchten, einen Reaktor zu entwickeln, der auch eine Voraussetzung für den Bau einer Plutonium‐Bombe gewesen wäre. Aber sie wussten nicht, wie eine Bombe realisiert werden kann, weil sie nie an einer realistischen Theorie der Atombombe gearbeitet hatten. Summary: Misinterpreted Documents and Ignored Physical Facts: The History of ‘Hitler's Atomic Bomb’ needs to be corrected. Why have the German physicists not developed an atomic bomb during World War II? For more than 25 years, the historians agree that they knew how to build the bomb, but that a bomb‐development programme of the size of the US‐Manhattan‐Project would not have been possible in wartime Germany. A detailed analysis of all preserved documents on the German atomic bomb research during the ‘Third Reich’, however, reveals considerable mistakes by the authors due to incomplete analysis of documents, misinterpretations of scientific explanations and ignoring of physical facts. It is shown that until the end of the war the German physicists did not know that an atomic bomb can only be made with fast neutrons, except Heisenberg, who, however, discovered it rather late, did not communicate it clearly and did not study any bomb physics. The physically correct interpretation of the documents reveals that the German physicists worked unsuccessfully on a reactor, which would have been a prerequisite for a plutonium bomb. But they did not know how to build a bomb because they never worked on a realistic bomb theory.
Autoimmunity and the microbiome: T‐cell receptor mimicry of “self” and microbial antigens mediates self tolerance in holobionts
Authors: Root‐Bernstein Robert
Published: September 2016

I propose a T‐cell receptor (TcR)‐based mechanism by which immunity mediates both “genetic self” and “microbial self” thereby, connecting microbiome disease with autoimmunity. The hypothesis is based on simple principles. First, TcR are selected to avoid strong cross‐reactivity with “self,” resulting in selection for a TcR repertoire mimicking “genetic self.” Second, evolution has selected for a “microbial self” that mimics “genetic self” so as to share tolerance. In consequence, our TcR repertoire also mimics microbiome antigenicity, providing a novel mechanism for modulating tolerance to it. Also, the microbiome mimics the TcR repertoire, acting as a secondary immune system. I call this TcR‐microbiome mimicry “holoimmunity” to denote immune tolerance to the “holobiont self.” Logically, microbiome‐host mimicry means that autoimmunity directed at host antigens will also attack components of the microbiome, and conversely, an immunological attack on the microbiome may cross‐react with host antigens producing “holoautoimmunity.”
Effect of polyamines on mechanical and structural properties of Bombyx mori silk
Authors: Yerra Aparna , Mysarla Danti Kumari , Siripurapu Prasanthi , Jha Anjali , Valluri Satyavathi V. , Mamillapalli Anitha
Published: September 2016

Silkworm, Bombyx mori (B. mori) belongs to the Lepidoptera family. The silk produced from this insect, mulberry silk, gained lot of importance as a fabric. Silk is being exploited as a biomaterial due to its surprising strength and biocompatibility. Polyamines (PA) are important cell growth regulators. In the present work the effect of treatment of polyamines, putrescine (Put), spermidine (Spd), and spermine (Spm) on the quantity and quality of silk produced was assessed. Results showed that exogenous feeding of Spd at a concentration of 50 µM increased fiber length significantly. Analysis by Fourier transform infrared (FTIR) on the properties of silk obtained from Spd treated silkworms revealed an increase in percentage of absorption with no difference in peak positions of amide I and amide III groups. Scanning electron microscopy (SEM) revealed an increase in diameter of silk. Further, analysis at molecular level showed an increase in fibroin expression in Spd treated silk glands. However, the Spd treatment showed no significant difference with respect to fibroin to sericin ratio per unit weight of cocoon, silk tenacity, and percent elongation. Thus, the present results show that polyamine treatment would influence silk quality at structural, mechanical, and molecular level in the Bombyx mori, which can be exploited in silk biomaterial production.
Do you take credit cards? The attitudinal and behavioral effects of advergames targeted at children
Authors: Naderer Brigitte , Matthes Jörg , Mestas Manina
Published: September 2016

Advergames are a promotional tool that confronts children with brands in an entertaining and playful setting. The present study adds to the existing knowledge by analyzing an advergame placement that is usually not targeted at children: credit cards. Based on an emotional conditioning process premised on the positive gaming experience, we argue that advergames lead to an increase in brand evaluation and brand choice. In addition to changes in brand outcomes, we investigate how playing a game promoting credit cards can impact children's spending behavior. For that purpose, children either played the traditional version of Monopoly paying with cash money or they played the banking version, promoting Visa credit cards. Results indicate that exposure to the branded game enhanced preference for Visa. In addition, children's spending behavior increased in an online shopping task. As another important contribution to the literature, we found the behavioral and attitudinal effects to be independent of children's age. In light of young consumers' high debt, our findings raise concerns about targeting children with credit card placements in advergames. Copyright © 2016 John Wiley & Sons, Ltd.