bluuebunny/crossref_metadata_2025 huggingface dataset:
Seasonal and diurnal variations in net carbon dioxide flux throughout the year from soil in paddy field
Authors: Nishimura Seiichi , Yonemura Seiichiro , Minamikawa Kazunori , Yagi Kazuyuki
Published: December 2014

In contrast to upland croplands, carbon dioxide (CO2) emission from soils has rarely been investigated previously in fields with paddy rice cultivation. In this study, we hypothesized that CO2 emission from paddy soils is suppressed to be a low level due the soil submergence for months for paddy rice cultivation and conducted a continuous measurement of net CO2 flux from the soil/water surface of a paddy field throughout the year, including both the submerged and drained periods. The net CO2 flux was generally near zero during the submerged period with paddy rice cultivation and showed a slight CO2 influx in the daytime and efflux at nighttime, indicating dominance of photosynthetic CO2 uptake and respiratory CO2 release by aquatic weeds and algae in paddy water. The diurnal variations in net CO2 flux and dissolved CO2 concentration had negative correlations with the pH of paddy water. A remarkably high CO2 efflux was observed during the period with intermittent drainage in summer. Unexpectedly, the cumulative CO2 emissions throughout the year were not considerably lower than those reported in upland croplands ranging from 1309 to 2160 g CO2 m−2 yr−1, of which 41–48% was emitted from the first drainage in summer to the rice harvest in autumn. In summary, in this study, we revealed that CO2 emission from soil in paddy fields is strictly suppressed during the submerged period, but considerably enhanced by the succeeding drainage, which may negate the suppressed CO2 emission during the submerged period.
Metal‐Organic Frameworks: Harmful Gas Removal
Authors: Liu Jian , McGrail B. Peter , Strachan Denis M. , Liu Jun , Tian Jian , Thallapally Praveen K.
Published: December 2014

Metal–organic frameworks (MOFs) have been considered to be novel adsorbents for a variety of applications, because of their high surface areas, large pore volumes, tunable pore geometries, and versatile chemical compositions. Besides their applications in energy gas storage, such as H
2
and CH
4
, harmful gas removal has become an important potential area for MOFs applications. This chapter reviews recent research related to four different types of harmful gas adsorption in MOFs, including greenhouse gases such as CO
2
, inorganic toxic gases such as SO

x

, NO

x

, and NH
3
; volatile organic compounds such as benzene and formaldehyde; and radioactive gases such as Xe, Kr, and I
2
. This information is organized in a way that will attempt to introduce this attractive research area to a broad audience, as well as to reveal some trends and significant discoveries to the researchers who are interested in this area. Obviously, removing harmful gases can provide a cleaner and safer living environment to human beings and other creatures. MOFs as novel adsorbents possess advantages, such as high gas adsorption capacities and selectivities, as well as adjustable properties to suit specific needs. However, more fundamental work is still necessary to understand this topic better, and some challenges, such as cost and stability, are in the way of applying MOFs to practical applications.
Metal‐Organic Frameworks: Photoreactive Frameworks
Authors: Chanthapally Anjana , Vittal Jagadese J.
Published: December 2014

This chapter deals with various photoreactive coordination polymers (CPs) and metal‐organic frameworks (MOFs) that undergo [2+2] cycloaddition reactions in the solid state, solid‐state structural transformations, post‐synthetic modification of surfaces creating reactive sites, radicals that are not possible by conventional synthetic routes, polymerization on the surfaces,cis‐transisomerization of the guest molecules in the cavities as well as the dynamic behavior of the CP and MOF structures. Further the formation of these compounds by photochemical methods is also discussed. The three‐dimensional (3D) structural characterization of the products of a number of photochemical and photo‐polymerization reactions were hampered by the lack of a suitable structural tool other than single crystal X‐ray crystallography. On the other hand, most of the examples discussed in this chapter do maintain single crystals at the end of the reactions such that 3D structural elucidation is possible by single crystal X‐ray crystallography to understand the reactivity completely. A few examples have been illustrated where [2+2] cycloaddition reaction has been used to monitor the formation of ladder structures in the solid state in the absence of crystal structures.
Metal–Organic Frameworks: Functional Magnetic Materials with Formate
Authors: Shang Ran , Chen Sa , Wang Zhe‐Ming , Gao Song
Published: December 2014

In this chapter, the state of art of the functional magnetic materials based on metal formate frameworks (MFFs), mainly developed in the past decade, is provided. These materials, belonging to a relatively small yet fundamentally important class of metal‐organic frameworks (MOFs), possess various structures and interesting properties. The binary or ternary dense MFFs display complicated structures and various magnetic behaviors though their constituents are simple. MFFs with ammonium components exhibited abundant and interesting magnetism, di‐/ferro‐/antiferroelectric and mechanical properties, structural phase transitions, and critical phenomena triggered by various order–disorder transitions of ammoniums, and the chirality, as well as the possible combinations such as multiferroics. These ammonium MFFs mimic the traditional inorganic materials such as perovskite, niccolite, and diamond. The porous diamondoid MFFs of [M3(HCOO)6] possess a wide spectrum of gas and guest inclusion behaviors. They thus show guest‐modulated magnetism, guest‐induced chirality, and guest‐based electric polarization. Mixing formate with coligands has provided MFFs with not only beautiful and fantastic structures but also interesting and appealing magnetic properties and others. It has been demonstrated that the formate, being the smallest and simple carboxylate, cheap and less toxic thus more biocompatible and environment‐friendly, and having been more or less ignored before, now comes back to our sight and awareness with its important role, having been verified, in the construction of promising MOF materials, and provides new materials with interesting properties.
Metal‐Organic Frameworks: Single‐Crystal‐to‐Single‐Crystal Transformations
Authors: Neogi Subhadip
Published: December 2014

Remarkable advances in the development of metal‐organic framework (MOF) structures have paved the way toward new multifunctional materials with various potential applications. Porous MOFs having flexible and dynamic properties, resulting from the cooperative action of organic and inorganic moieties, represent an important subclass. Changes between the solid phases under external stimuli are particularly intriguing especially when crystallinity is maintained, allowing direct visualization of such changes via X‐ray crystallography. This chapter is concerned with such changes under different types of external stimuli in single‐crystal to single‐crystal (SC–SC) manner, with an ultimate hope to open up new dimensions in materials chemistry.
Predicting aggressive behavior with the aggressiveness‐IAT
Authors: Banse Rainer , Messer Mario , Fischer Ilka
Published: December 2014

The Implicit Association Test (IAT, Greenwald, McGhee, & Schwartz, 1998) was adapted to assess the automatically activated (implicit) self‐concept of aggressiveness. In three studies the validity of the Aggressiveness‐IAT (Agg‐IAT) was supported by substantial correlations with self‐report measures of aggressiveness. After controlling for self‐report measures of aggressiveness, the Agg‐IAT accounted for 9–15% of the variance of three different indicators of aggressive behavior across three studies. To further explore the nomological network around the Agg‐IAT we investigated its correlations with measures of social desirability (SD). Although not fully conclusive, the results across four studies provided some support for a weak negative correlation between impression management SD and aggressive behavior as well as the Agg‐IAT. This result is in line with an interpersonally oriented self‐control account of impression management SD. Individuals with high SD scores seem to behave less aggressively, and to show lower Agg‐IAT scores. The one‐week stability of the Agg‐IAT was r = .58 in Study 4. Aggr. Behav. 41:65–83 2015. © 2014 Wiley Periodicals, Inc.
Self‐Powered Trajectory, Velocity, and Acceleration Tracking of a Moving Object/Body using a Triboelectric Sensor
Authors: Yi Fang , Lin Long , Niu Simiao , Yang Jin , Wu Wenzhuo , Wang Sihong , Liao Qingliang , Zhang Yue , Wang Zhong Lin
Published: December 2014

Motion tracking is of great importance in a wide range of fields such as automation, robotics, security, sports and entertainment. Here, a self‐powered, single‐electrode‐based triboelectric sensor (TES) is reported to accurately detect the movement of a moving object/body in two dimensions. Based on the coupling of triboelectric effect and electrostatic induction, the movement of an object on the top surface of a polytetrafluoroethylene (PTFE) layer induces changes in the electrical potential of the patterned aluminum electrodes underneath. From the measurements of the output performance (open‐circuit voltage and short‐circuit current), the motion information about the object, such as trajectory, velocity, and acceleration is derived in conformity with the preset values. Moreover, the TES can detect motions of more than one objects moving at the same time. In addition, applications of the TES are demonstrated by using LED illuminations as real‐time indicators to visualize the movement of a sliding object and the walking steps of a person.
Optimal design and operations of supply chain networks for water management in shale gas production: MILFP model and algorithms for the water‐energy nexus
Authors: Gao Jiyao , You Fengqi
Published: December 2014

The optimal design and operations of water supply chain networks for shale gas production is addressed. A mixed‐integer linear fractional programming (MILFP) model is developed with the objective to maximize profit per unit freshwater consumption, such that both economic performance and water‐use efficiency are optimized. The model simultaneously accounts for the design and operational decisions for freshwater source selection, multiple transportation modes, and water management options. Water management options include disposal, commercial centralized wastewater treatment, and onsite treatment (filtration, lime softening, thermal distillation). To globally optimize the resulting MILFP problem efficiently, three tailored solution algorithms are presented: a parametric approach, a reformulation‐linearization method, and a novel Branch‐and‐Bound and Charnes–Cooper transformation method. The proposed models and algorithms are illustrated through two case studies based on Marcellus shale play, in which onsite treatment shows its superiority in improving freshwater conservancy, maintaining a stable water flow, and reducing transportation burden. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1184–1208, 2015
Nasal and bronchial response to exercise in children with seasonal allergic rhinitis out of the pollen season
Authors: Harmancı Koray , Urhan Barıs , Anıl Hülya , Kocak Abdulkadır
Published: December 2014

Background

Allergic rhinitis is a type I allergic disease of the nasal mucosa, and is characterized by paroxysmal sneezing, watery rhinorrhea, and nasal blockage. In seasonal allergic rhinitis subjects, even subthreshold allergen doses have been found to cause inflammatory cell infiltration in the nasal mucosa. This study aimed to investigate the presence of nasal obstructions and symptoms in seasonal allergic rhinitis subjects by assessing an exercise challenge test (ECT) outside of the pollen season.

Methods

Twenty patients and 20 healthy children who were admitted to the Osmangazi University Medical School Pediatric Allergy Clinic were included in the study in a pollen free season. The total nasal airflow and visual analog scale (for rhinorrhea, nasal congestion, sneezing, and itching) and pulmonary function tests were evaluated before and after each ECT. The nasal airflow and resistance changes were evaluated with anterior rhinomanometry.

Results

Eight patients and one healthy child had nasal obstructions after the ECT. There was a significant difference in the exercise‐induced nasal obstructions between the 2 groups (p = 0.02). Eighteen children with exposure to tobacco smoke in the patient and control groups had lower forced expiratory volume in 1 second (FEV1), forced vital capacity (FVC), and forced expiratory flow 25% to 75% (FEF25‐75) values than the children without exposure to tobacco smoke.

Conclusion

The prevalence of exercise‐induced nasal obstruction in children with seasonal rhinitis out of the pollen season is 40%. We showed that minimal persistent inflammation and nasal symptoms can also be diagnosed in rhinitis children in a symptom‐free period.
Covalent Modification of a Cysteine Residue in the XPB Subunit of the General Transcription Factor TFIIH Through Single Epoxide Cleavage of the Transcription Inhibitor Triptolide
Authors: He Qing‐Li , Titov Denis V. , Li Jing , Tan Minjia , Ye Zhaohui , Zhao Yingming , Romo Daniel , Liu Jun O.
Published: December 2014

Triptolide is a key component of the traditional Chinese medicinal plant Thunder God Vine and has potent anticancer and immunosuppressive activities. It is an irreversible inhibitor of eukaryotic transcription through covalent modification of XPB, a subunit of the general transcription factor TFIIH. Cys342 of XPB was identified as the residue that undergoes covalent modification by the 12,13‐epoxide group of triptolide. Mutation of Cys342 of XPB to threonine conferred resistance to triptolide on the mutant protein. Replacement of the endogenous wild‐type XPB with the Cys342Thr mutant in a HEK293T cell line rendered it completely resistant to triptolide, thus validating XPB as the physiologically relevant target of triptolide. Together, these results deepen our understanding of the interaction between triptolide and XPB and have implications for the future development of new analogues of triptolide as leads for anticancer and immunosuppressive drugs.
Near‐IR Phosphorescent Ruthenium(II) and Iridium(III) Perylene Bisimide Metal Complexes
Authors: Schulze Marcus , Steffen Andreas , Würthner Frank
Published: December 2014

The phosphorescence emission of perylene bisimide derivatives has been rarely reported. Two novel ruthenium(II) and iridium(III) complexes of an azabenz‐annulated perylene bisimide (ab‐PBI), [Ru(bpy)2(ab‐PBI)][PF6]2 1 and [Cp*Ir(ab‐PBI)Cl]PF6 2 are now presented that both show NIR phosphorescence between 750–1000 nm in solution at room temperature. For an NIR emitter, the ruthenium complex 1 displays an unusually high quantum yield (Φp) of 11 % with a lifetime (τp) of 4.2 μs, while iridium complex 2 exhibits Φp<1 % and τp=33 μs. 1 and 2 are the first PBI‐metal complexes in which the spin–orbit coupling is strong enough to facilitate not only the Sn→Tn intersystem crossing of the PBI dye, but also the radiative T1→S0 transition, that is, phosphorescence.
Reactions of Difunctional Electrophiles with Functionalized Aryllithium Compounds: Remarkable Chemoselectivity by Flash Chemistry
Authors: Nagaki Aiichiro , Imai Keita , Ishiuchi Satoshi , Yoshida Jun‐ichi
Published: December 2014

Flash chemistry using flow microreactors enables highly chemoselective reactions of difunctional electrophiles with functionalized aryllithium compounds by virtue of extremely fast micromixing. The approach serves as a powerful method for protecting‐group‐free synthesis using organolithium compounds and opens a new possibility in the synthesis of polyfunctional organic molecules.
Screening for Protein Phosphorylation Using Nanoscale Reactions on Microdroplet Arrays
Authors: Küster Simon K. , Pabst Martin , Zenobi Renato , Dittrich Petra S.
Published: December 2014

We present a novel and straightforward screening method to detect protein phosphorylations in complex protein mixtures. A proteolytic digest is separated by a conventional nanoscale liquid chromatography (nano‐LC) separation and the eluate is immediately compartmentalized into microdroplets, which are spotted on a microarray MALDI plate. Subsequently, the enzyme alkaline phosphatase is applied to every second microarray spot to remove the phosphate groups from phosphorylated peptides, which results in a mass shift of n×−80 Da. The MALDI‐MS scan of the microarray is then evaluated by a software algorithm to automatically identify the phosphorylated peptides by exploiting the characteristic chromatographic peak profile induced by the phosphatase treatment. This screening method does not require extensive MS/MS experiments or peak list evaluation and can be easily extended to other enzymatic or chemical reactions.
Highly Regio‐ and Enantioselective Synthesis of N‐Substituted 2‐Pyridones: Iridium‐Catalyzed Intermolecular Asymmetric Allylic Amination
Authors: Zhang Xiao , Yang Ze‐Peng , Huang Lin , You Shu‐Li
Published: December 2014

The first iridium‐catalyzed intermolecular asymmetric allylic amination reaction with 2‐hydroxypyridines has been developed, thus providing a highly efficient synthesis of enantioenriched N‐substituted 2‐pyridone derivatives from readily available starting materials. This protocol features a good tolerance of functional groups in both the allylic carbonates and 2‐hydroxypyridines, thereby delivering multifunctionalized heterocyclic products with up to 98 % yield and 99 % ee.
Effect of treatment pressure on structures and properties of PMIA fiber in supercritical carbon dioxide fluid
Authors: Zheng Huanda , Zhang Juan , Du Bing , Wei Qufu , Zheng Laijiu
Published: December 2014

The effects of treatment pressure on the structures and properties of PMIA fiber were investigated by Scanning electron microscopy, Dynamic wetting measurements, Fourier transform infrared spectrometry, X‐ray diffraction, thermogravimetric analysis, and mechanical properties test technology in supercritical carbon dioxide. The results indicated that the surface morphology, the water contact angle, the interaction of macromolecules, the crystal structure, the thermal property, and tensile strength of PMIA fibers were changed during supercritical carbon dioxide treatment, particularly the surface morphology and the wettability of fiber changed the most obviously with the increase of treatment pressure. Furthermore, the thermal property and tensile strength of treated PMIA fiber sample were improved in comparison with those of untreated sample. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41756.
A high cell density transient transfection system for therapeutic protein expression based on a CHO GS‐knockout cell line: Process development and product quality assessment
Authors: Rajendra Yashas , Hougland Maria D. , Alam Riazul , Morehead Teresa A. , Barnard Gavin C.
Published: December 2014

Transient gene expression (TGE) is a rapid method for the production of recombinant proteins in mammalian cells. While the volumetric productivity of TGE has improved significantly over the past decade, most methods involve extensive cell line engineering and plasmid vector optimization in addition to long fed batch cultures lasting up to 21 days. Our colleagues have recently reported the development of a CHO K1SV GS‐KO host cell line. By creating a bi‐allelic glutamine synthetase knock out of the original CHOK1SV host cell line, they were able to improve the efficiency of generating high producing stable CHO lines for drug product manufacturing. We developed a TGE method using the same CHO K1SV GS‐KO host cell line without any further cell line engineering. We also refrained from performing plasmid vector engineering. Our objective was to setup a TGE process to mimic protein quality attributes obtained from stable CHO cell line. Polyethyleneimine (PEI)‐mediated transfections were performed at high cell density (4 × 106 cells/mL) followed by immediate growth arrest at 32°C for 7 days. Optimizing DNA and PEI concentrations proved to be important. Interestingly, found the direct transfection method (where DNA and PEI were added sequentially) to be superior to the more common indirect method (where DNA and PEI are first pre‐complexed). Moreover, the addition of a single feed solution and a polar solvent (N,N dimethylacetamide) significantly increased product titers. The scalability of process from 2 mL to 2 L was demonstrated using multiple proteins and multiple expression volumes. Using this simple, short, 7‐day TGE process, we were able to successfully produce 54 unique proteins in a fraction of the time that would have been required to produce the respective stable CHO cell lines. The list of 54 unique proteins includes mAbs, bispecific antibodies, and Fc‐fusion proteins. Antibody titers of up to 350 mg/L were achieved with the simple 7‐day process. Titers were increased to 1 g/L by extending the culture to 16 days. We also present two case studies comparing product quality of material generated by transient HEK293, transient CHO K1SV GS‐KO, and stable CHO K1SV KO pool. Protein from transient CHO was more representative of stable CHO protein compared to protein produced from HEK293. Biotechnol. Bioeng. 2015;112: 977–986. © 2014 Wiley Periodicals, Inc.
The biotechnological potential of subtilisin‐like fibrinolytic enzyme from a newly isolated Lactobacillus plantarum KSK‐II in blood destaining and antimicrobials
Authors: Kotb Essam
Published: December 2014

An antimicrobial oxidative‐ and SDS‐stable fibrinolytic alkaline protease designated as KSK‐II was produced by Lactobacillus plantarum KSK‐II isolated from kishk, a traditional Egyptian food. Maximum enzyme productivity was obtained in medium containing 1% lactose and 0.5% soybean flour as carbon and nitrogen sources, respectively. Purification of enzyme increased its specific activity to 1,140‐fold with a recovery of 33% and molecular weight of 43.6 kDa. Enzyme activity was totally lost in the presence of ethylenediaminetetraacetic acid and was restored after addition of Fe2+ suggesting that KSK‐II is a metalloprotease and Fe2+ acts as cofactor. Enzyme hydrolyzed not only the natural proteins but also synthetic substrates, particularly Suc‐Ala‐Ala‐Pro‐Phe‐pNA. KSK‐II can hydrolyze the Lys‐X easier than Arg‐X; thus, it was considered as a subtilisin‐family protease. Its apparent Km, Vmax, and Kcat were 0.41 mM, 6.4 µmol mg−1 min−1, and 28.0 s−1, respectively. KSK‐II is industrially important from the perspectives of its maximal activity at 50°C (stable up to 70°C), ability to function at alkaline pH (10.0), stability at broad pH ranges (7.5–12.0) in addition to its stability toward SDS, H2O2, organic solvents, and detergents. We emphasize for the first time the potential of fibrinolytic activity for alkaline proteases used in detergents especially in blood destaining. © 2014 American Institute of Chemical Engineers Biotechnol. Prog., 31:316–324, 2015
Development and deployment of a new robotics toolbox for education
Authors: Gil Arturo , Reinoso Oscar , Marin Jose Maria , Paya Luis , Ruiz Javier
Published: December 2014

This paper presents a new toolbox focussed on the teaching of robotic manipulators. The library works under Matlab and has been designed to strengthen the theoretical concepts explained during the theory lectures. The educational approach is focussed on teaching the main concepts through developing math modeling and simulation. In order to do this, the toolbox aims at the fulfillment of a set of practical sessions that allow the students to test most of the concepts of an introductory course in robotic manipulators. In addition, the library possesses features that typically needed the usage of proprietary software, such as the visualization of a realistic 3D representation of commercial robotic arms and the programming of those arms in an industrial language. The practices include the concepts of direct and inverse kinematics, inverse and direct dynamics, path planning and robot programming. As a transversal practice, during the sessions, the student is asked to choose and integrate a new robotic arm in the library, proposing a particular solution to the direct and inverse kinematic problem, as well as the inclusion of other important parameters. The library has been deployed during the last year in bachelor and master studies and has received a nice acceptance. Finally, the library has been assessed in terms of usefulness, design and usage by means of a student survey. In addition, the surveys were designed to establish a relation between the student perception of the system, the time spent on the tool and their learning achievements. © 2014 Wiley Periodicals, Inc. Comput Appl Eng Educ 23:443–454, 2015; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21615
Foreign brands in local cultures: A socio‐cultural perspective of postmodern brandscapes
Authors: Al‐Mutawa Fajer Saleh , Elliott Richard , Nuttall Peter
Published: December 2014

The aim of this paper is to explore how the consumption of foreign brands may operate in a local culture (specifically, the consumption of Western luxury fashion brands among Muslim women in Kuwait). Field observations were conducted in Kuwait, and a qualitative questionnaire was administered to 50 Muslim female consumers. Although not a common method for qualitative research, the benefits of using a qualitative questionnaire are highlighted. The findings show that the socio‐cultural dynamics in Kuwait (mainly religion and tradition) may restrict the expression of certain behaviour (such as female sexuality and dating). However, Muslim women make use of Western luxury fashion brands as postmodern brandscapes (fragmented and constantly negotiated use of a symbolic brand to actively construct lifestyle orientations and personal meanings among one's neo‐tribe) to manifest their expressions of sexuality in alternative ways. Copyright © 2014 John Wiley & Sons, Ltd.
Bio‐Inspired Transition Metal–Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory
Authors: McSkimming Alex , Chan Bun , Bhadbhade Mohan M. , Ball Graham E. , Colbran Stephen B.
Published: December 2014

Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI+) organic hydride‐acceptor domain has been coupled with a 1,10‐phenanthroline (phen) metal‐binding domain to afford a novel multifunctional ligand (LBI+) with hydride‐carrier capacity (LBI++H−⇌LBIH). Complexes of the type [Cp*M(LBI)Cl][PF6]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the IrIII congener, X‐ray crystallography. [Cp*Rh(LBI)Cl][PF6]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir(LBI)Cl][PF6] and [Cp*M(phen)Cl][PF6] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate‐driven RhH formation (90 kJ mol−1 free‐energy barrier), transfer of hydride between the Rh and BI+ centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back‐transfer of hydride from the BIH organic hydride donor to the Rh‐activated imine substrate (89 kJ mol−1 barrier), and exergonic protonation of the metal‐bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed.
Synthesis and Characterization of a Biotinylated Multivalent Targeted Contrast Agent
Authors: Gündüz Serhat , Power Anthony , Maier Martin E. , Logothetis Nikos K. , Angelovski Goran
Published: December 2014

A new bimodal and multivalent dendritic contrast agent (CA) that targets the protein avidin was prepared and characterized. The tripartite lysine core was used to link the ligand biotin, the fluorescent dye, and the dendron carrying GdDOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid) chelates for amplification of the magnetic resonance imaging (MRI) signal. The longitudinal relaxivity of this dendrimeric CA was greater than those of its GdDOTA chelate and most of the common commercial agents at the investigated high magnetic field (7 T). The capacity of the dendrimeric CA to bind to the target protein was confirmed by fluorescence measurements upon its treatment with NeutrAvidin–agarose gel or NeutrAvidin‐coated microspheres and the results were compared with those of its monomeric analogue. The fluorescence intensity of monomer‐treated targets was found to be greater than that from those treated with dendrimeric CA; however, a several‐fold increase in the MRI signal was observed on the same samples treated with the dendrimeric CA. The inductively coupled plasma mass spectrometry analysis of the digested samples indicated somewhat higher Gd3+ content and hence slightly better binding of monomeric versus dendrimeric CA. This bimodal and multivalent targeted probe opens an avenue for the preparation of new nanosized CAs that allow high‐resolution MRI of various targets, such as cellular receptors or specific cellular populations.
Bemessungsbeispiele – Nachweisführung nach dem vereinfachten Verfahren
Authors: Schermer Detleff
Published: December 2014

Die Regelungen im vereinfachten Verfahren von Eurocode 6, Teil 3 [4] mit dem zugehörigen Nationalen Anhang erlauben es, in wenigen Schritten rechnerische Nachweise von Mauerwerksbauteilen durchzuführen. Anhand mehrerer Bauteilnachweise aus der Praxis wird im Folgenden die Nachweisführung nach dem vereinfachten Verfahren dargestellt. Es ist erkennbar, dass bei Einhaltung der Anforderungen an das vereinfachte Verfahren sich die rechnerische Nachweisführung sehr einfach gestaltet und der größte Zeitaufwand in der Lastermittlung der einzelnen Bauteile liegt. Eine weitere Vereinfachung, die jedoch etwas stärkere Einschränkungen des Anwendungsbereiches bedingt, ist durch das im Anhang A angegebene sog. stark vereinfachte Verfahren gegeben.

Design examples – Analysis according to simpified calculation methods. Using the simplified calculation methods for unreinforced masonry structures of Eurocode 6‐3 is a very quick and easy way to design unreinforced masonry structures. In the following paper several examples of the design of strucutral members are given. Practical experience shows that the main effort of the design process results from the structural analysis and the determination of the axial force in the masonry walls. A further simplification ist possible for strucutres according to annex A.
Synthesis of Monodisperse SrTi1–xZrxO3 Nanocubes in Oleate by a Two‐Phase Solvothermal Method
Authors: Friderichs Christian , Zotov Nikolay , Mader Werner
Published: December 2014

Nanocubes of mixed‐crystal perovskites SrTi1–xZrxO3 (x = 0.25–0.6) were obtained in a two‐phase oil/water solvothermal environment. In an optically transparent autoclave, the evolution of an alkali metal oleate phase at the oil/water interface was monitored; this phase is the environment for nucleation and growth of the nanocrystals. The typical synthesis yields monodisperse nanocubes with an edge length of 10 nm. The size and shape of the nanoparticles do not depend on the Zr content and, most remarkably, do not vary with reaction time. We propose a growth mechanism that depends on the accessibility of the metal hydroxyalkanoate monomers to the growing crystal: after the formation of {100} facets, they are densely capped by oleate ion surfactants, and monomers are no longer able to attach. Increasing the reaction time only increases the amount of nanoparticles formed. As determined by Raman spectroscopy and energy‐dispersive X‐ray spectroscopy, the nanoparticles have the cubic (Pm$\bar {3}$m) perovskite structure and have an excess of B‐site ions (Ti + Zr), which is explained by a terminating Ti/Zr + O surface layer of the nanocubes. The monodisperse particles self‐assemble to form monolayers on a support.
Photo‐ and Electrocatalytic Reduction of CO2 by [Re(CO)3{α,α′‐Diimine‐(4‐piperidinyl‐1,8‐naphthalimide)}Cl] Complexes
Authors: Franco Federico , Cometto Claudio , Garino Claudio , Minero Claudio , Sordello Fabrizio , Nervi Carlo , Gobetto Roberto
Published: December 2014

The effects of the highly fluorescent 4‐piperidinyl‐1,8‐naphthalimide (PNI) chromophore on the CO2 reduction catalytic properties of rhenium‐based catalysts are investigated herein. In particular, the electro‐ and photocatalytic CO2 reduction features of [Re(CO)3(bpy)Cl] (bpy = 2,2′‐bipyridine) are compared with the activity of [Re(CO)3(phen–PNI)Cl] (phen = 1,10‐phenanthroline), which is known for its long excited‐state lifetime. Moreover, another Re complex, namely [Re(CO)3(bpy–Ph–PNI)Cl], has been synthesized and tested as an electro‐ and photocatalyst. The catalytic properties of the selected compounds were studied by means of electrochemical (cyclic voltammetry and controlled‐potential electrolysis) and photophysical measurements together with DFT calculations. [Re(CO)3(bpy–Ph–PNI)Cl] showed good electrocatalytic efficiency toward selective CO2 reduction to CO, as well as reduced electrocatalytic overpotential.
Transition‐Metal‐Free Synthesis of Fluorinated Nitriles and Diaryl Ketones Through a Selective C–F Bond Functionalization Under Mild Conditions
Authors: Yang Guang‐Hui , Liu Ming , Li Na , Wu Ran , Chen Xu , Pan Ling‐Ling , Gao Shang , Huang Xing , Wang Chen , Yu Chuan‐Ming
Published: December 2014

A highly efficient and simple procedure was developed to synthesize substituted fluorinated nitriles and diaryl ketones under mild conditions from polyfluorobenzenes and phenylacetonitriles. This coupling process was achieved by using a selective C–F bond functionalization without a transition‐metal catalyst. The reactions had good functional group tolerance and provided the products in moderate to excellent yields.
Supercritical Fluid Extraction of Bio‐oils from Hawthorn Stones: A Box–Behnken Design for the Extraction Parameters
Authors: Akalın Mehmet Kuddusi , Akyüz Mehmet , Karagöz Selhan
Published: December 2014

Hawthorn stones, a waste biomass, were subjected to supercritical ethanol extraction to obtain bio‐oils. Optimization of the extraction parameters was performed according to the Box–Behnken design to estimate the effects of extraction temperature, extraction time, and biomass concentration on the yields of the bio‐oil and the conversion of the biomass. High correlation coefficients (R2) were obtained. The values of R2 were 0.90 and 0.98 % for bio‐oil and biomass conversion, respectively. The validity of the model used in this procedure was indicated by the consistent matching of predicted values with the experimental values. The experimental results demonstrated that the optimized conditions fell within the range of the experimental design.
A pilot randomized controlled trial evaluating an integrated treatment of rivastigmine transdermal patch and cognitive stimulation in patients with Alzheimer's disease
Authors: D'Onofrio Grazia , Sancarlo Daniele , Addante Filomena , Ciccone Filomena , Cascavilla Leandro , Paris Francesco , Elia Anna Chiara , Nuzzaci Claudia , Picoco Michele , Greco Antonio , Panza Francesco , Pilotto Alberto
Published: December 2014

Objective

To evaluate in a pilot single‐blind randomized controlled clinical trial the efficacy of an integrated treatment with rivastigmine transdermal patch (RTP) and cognitive stimulation (CS) in Alzheimer's disease (AD) patients at 6‐month follow‐up.

Methods

We enrolled 90 patients with an age ≥65 years admitted to the outpatient Alzheimer's Evaluation Unit with diagnosis of AD. Patients were randomized to enter in the Group‐1 (RTP + CS) or in the Group‐2 (RTP). All patients at baseline and after 6 months were evaluated with the following tools: Mini Mental State Examination (MMSE), Clinical Dementia Rating (CDR), Hamilton Rating Scale for Depression (HAM‐D), Geriatric Depression Scale (GDS‐15), Neuropsychiatric Inventory (NPI), Neuropsychiatric Inventory‐Distress (NPI‐D), and a standardized Comprehensive Geriatric Assessment, including also activities of daily living (ADL), instrumental activities of daily living (IADL), and the Mini Nutritional Assessment (MNA). Mortality risk was assessed using the Multidimensional Prognostic Index (MPI).

Results

At baseline no significant difference was shown between the two groups. After 6 months of follow‐up, there were significant differences between Group‐1 and Group‐2 in: MMSE: +6.39% vs. +2.69%, CDR: +6.92% vs. +1.54%, HDRS‐D = −60.7% vs. −45.8%, GDS: −60.9% vs. −7.3%, NPI: −55.2% vs. −32.7%%, NPI‐D: −55.1% vs. −18.6%, ADL: +13.88% vs. +5.95%, IADL: +67.59% vs. +18.28%, MNA: +12.02% vs. +5.91%, and MPI: −29.03% vs. −12.90%.

Conclusion

The integrated treatment of RTP with CS in AD patients for 6 months improved significantly cognition, depressive and neuropsychiatric symptoms, functional status, and mortality risk in comparison with a group of AD patients receiving only RTP. Copyright © 2014 John Wiley & Sons, Ltd.
On computation of strain‐dependent permeability of rocks and rock‐like porous media
Authors: Shin Hyu Soung , Kim Kwang Yeom , Pande Gyan N.
Published: December 2014

Determination of transport properties of geomaterials is an important issue in many fields of engineering analysis and design. For example, in petroleum engineering, in situ permeability of an oil reservoir may be crucial in establishing its viability for exploitation, whilst prevention of leakage from underground storage facilities for oil and gas, nuclear waste as well as viability of CO2 sequestration projects crucially depends on its long‐term values. Permeability is indirectly related to the porosity, pore‐size distribution and pore architecture of the porous media. These parameters evolve when a strain field is imposed. Physical measurement of permeability under a strain field in laboratory conditions is difficult, expensive and prone to a number of uncertainties. In the past, pore network models have been used to compute permeability of materials under stress/strain‐free conditions. In this paper, we propose an enhanced pore network model to compute permeability of rocks and rock‐like porous media under a stress/strain field. Data of pore‐size distribution obtained from mercury intrusion porosimetry are used to compute permeability of rock samples from various unspecified oilfields in the world. It is shown that the two permeabilities can be predicted from the model with sufficient accuracy. A hypothesis for change in porosity, pore‐size distribution and pore architecture as a result of imposed mechanical strains is then proposed. Based on this, permeability is computed again for one of the rock samples under uniaxial and triaxial compressive and tensile strain fields. It is shown that depending on the state of strain field imposed, permeability evolves in an anisotropic manner. Permeability under tensile strain field increases dramatically compared with the reduction that takes place under compressive strain field of the same magnitude. Copyright © 2014 John Wiley & Sons, Ltd.
A medial‐axis‐based model for propagating cracks in a regularised bulk
Authors: Tamayo‐Mas Elena , Rodríguez‐Ferran Antonio
Published: December 2014

A new continuous‐discontinuous strategy for the simulation of failure is presented. The continuous bulk is regularised by means of a gradient‐enhanced damage model, where non‐locality is introduced at the level of displacements. As soon as the damage parameter is close or equal to 1, a traction‐free crack is introduced. To determine the direction of crack growth, a new criterion is proposed. In contrast to traditional techniques, where mechanical criteria are used to define the crack path, here, a geometrical approach is used. More specifically, given a regularised damage field D(x), we propose to propagate the discontinuity following the direction dictated by the medial axis of the isoline (or isosurface in 3D) D(x) = D*. The proposed approach is tested on different two‐dimensional and three‐dimensional examples that illustrate that this combined methodology is able to deal with damage growth and material separation. Copyright © 2014 John Wiley & Sons, Ltd.
General topology optimization method with continuous and discrete orientation design using isoparametric projection
Authors: Nomura Tsuyoshi , Dede Ercan M. , Lee Jaewook , Yamasaki Shintaro , Matsumori Tadayoshi , Kawamoto Atsushi , Kikuchi Noboru
Published: December 2014

A general topology optimization method, which is capable of simultaneous design of density and orientation of anisotropic material, is proposed by introducing orientation design variables in addition to the density design variable. In this work, the Cartesian components of the orientation vector are utilized as the orientation design variables. The proposed method supports continuous orientation design, which is out of the scope of discrete material optimization approaches, as well as design using discrete angle sets. The advantage of this approach is that vector element representation is less likely to fail into local optima because it depends less on designs of former steps, especially compared with using the angle as a design variable (Continuous Fiber Angle Optimization) by providing a flexible path from one angle to another with relaxation of orientation design space. An additional advantage is that it is compatible with various projection or filtering methods such as sensitivity filters and density filters because it is free from unphysical bound or discontinuity such as the one at θ = 2π and θ = 0 seen with direct angle representation. One complication of Cartesian component representation is the point‐wise quadratic bound of the design variables; that is, each pair of element values has to reside in a given circular bound. To overcome this issue, we propose an isoparametric projection method, which transforms box bounds into circular bounds by a coordinate transformation with isoparametric shape functions without having the singular point that is seen at the origin with polar coordinate representation. A new topology optimization method is built by taking advantage of the aforementioned features and modern topology optimization techniques. Several numerical examples are provided to demonstrate its capability. Copyright © 2014 John Wiley & Sons, Ltd.
Polarization‐maintaining Fiber Optics
Authors: Krischke Anja , Knothe Christian , Oechsner Ulrich
Published: December 2014

A stable measurement setup is fundamental for any successful measurement. A major cause of frustration and error is the need to continuously readjust optomechanical equipment because of continuous instabilities. The use of fiber optics has proven to increase both stability and convenience significantly when compared with standard free‐beam setups. These modular, complex and self‐contained setups also often increase laser safety and reduce the laser safety classification. The defined interface between a laser source and the more sensitive environment of the measurement setup provides the physical separation that enables a mechanical and thermal decoupling, suppressing mutually negative effects.
Recent advances in targeted proteomics for clinical applications
Authors: Domon Bruno , Gallien Sebastien
Published: December 2014

MS‐based approaches using targeted methods have been widely adopted by the proteomics community to study clinical questions such as the evaluation of biomarkers. At present, the most widely used targeted MS method is the SRM technique typically performed on a triple quadrupole instrument. However, the high analytical demands for performing clinical studies in combination with the extreme complexity of the samples involved are a serious challenge. The segmentation of the biomarker evaluation workflow has only partially alleviated these issues by differently balancing the analytical requirements and throughput at different stages of the process. The recent introduction of targeted high‐resolution and accurate‐mass analyses on fast sequencing mass spectrometers operated in parallel reaction monitoring (PRM) mode offers new avenues to conduct clinical studies and thus overcome some of the limitations of the triple quadrupole instrument. This article discusses the attributes and specificities of the PRM technique, in terms of experimental design, execution, and data analysis, and the implications for biomarker evaluation. The benefits of PRM on data quality and the impact on the consistency of results are highlighted and the definitive progress on the overall output of clinical studies, including high throughput, is discussed.
Quantitative analysis of polyhexamethylene guanidine (PHMG) oligomers via matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry with an ionic‐liquid matrix
Authors: Yoon Donhee , Lee Dongkun , Lee Jong‐Hyeon , Cha Sangwon , Oh Han Bin
Published: December 2014

RATIONALE

Quantifying polymers by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOFMS) with a conventional crystalline matrix generally suffers from poor sample‐to‐sample or shot‐to‐shot reproducibility. An ionic‐liquid matrix has been demonstrated to mitigate these reproducibility issues by providing a homogeneous sample surface, which is useful for quantifying polymers. In the present study, we evaluated the use of an ionic liquid matrix, i.e., 1‐methylimidazolium α‐cyano‐4‐hydroxycinnamate (1‐MeIm‐CHCA), to quantify polyhexamethylene guanidine (PHMG) samples that impose a critical health hazard when inhaled in the form of droplets.

METHODS

MALDI‐TOF mass spectra were acquired for PHMG oligomers using a variety of ionic‐liquid matrices including 1‐MeIm‐CHCA. Calibration curves were constructed by plotting the sum of the PHMG oligomer peak areas versus PHMG sample concentration with a variety of peptide internal standards.

RESULTS

Compared with the conventional crystalline matrix, the 1‐MeIm‐CHCA ionic‐liquid matrix had much better reproducibility (lower standard deviations). Furthermore, by using an internal peptide standard, good linear calibration plots could be obtained over a range of PMHG concentrations of at least 4 orders of magnitude.

CONCLUSIONS

This study successfully demonstrated that PHMG samples can be quantitatively characterized by MALDI‐TOFMS with an ionic‐liquid matrix and an internal standard. Copyright © 2014 John Wiley & Sons, Ltd.
Coordinative Saturation of the Pterin Heterocycle by Ferrocenylcopper(I) Complex Fragments
Authors: Jana Rajkumar , Lissner Falk , Kaim Wolfgang
Published: December 2014

2‐Pivaloylpterin, an acylated derivative of the biochemically relevant pterin [2‐amino‐4‐oxo‐(3H)pteridine] heterocyclus, undergoes stepwise metallation by the 1, 1′‐bis(diphenylphosphanyl)ferrocene‐copper(I) cation, [(dppf)Cu]+. The final product obtained, [Cu3(dppf)(μ2‐dppf)(PP)(PP‐H+)]2(BF4)4, could be structurally characterized to reveal coordinative saturation with binding of central Cu+ ions to N1,N3,O4,N5,N8 and pivaloyl‐O donor atoms.