bluuebunny/crossref_metadata_2025 huggingface dataset:
Catalytic Epoxidation of Organics from Vegetable Sources
Authors: Guidotti Matteo , Palumbo Chiara
Published: September 2016

Unsaturated fatty acids, fatty acid esters, and terpenes are alkenic molecules that can be extracted directly from vegetable sources and converted into a broad range of intermediates, commodities, and high value‐added products by means of epoxidation reactions. Conventional stoichiometric epoxidation techniques using environmentally unfriendly oxidants are still performed at the industrial scale. However, several examples, at the laboratory level, show how it is possible to use more sustainable oxidants, such as alkyl hydroperoxides, hydrogen peroxide or, in the best cases, molecular oxygen, in the presence of catalytic systems. Homogeneous, heterogeneous, enzymatic catalysts or, even, metal‐free organocatalysts can help in avoiding the use of hazardous oxidants and noxious solvents and in performing an efficient, selective, and safe epoxidation of C=C bonds in oils, fatty derivatives, and terpenic compounds.
Challenges in Green Analytical Chemistry
Authors: Garrigues Salvador , Armenta Sergio , de la Guardia Miguel
Published: September 2016

The challenges on Green Inorganic Analysis, in the frame of a sustainable analytical chemistry free from the deleterious side effects of the analytical practices, are presented and discussed. Special attention will be paid on the evaluation of the method greenness, the different approaches available in the scientific literature to do inorganic analysis, the inorganic materials used as analytical tools and their synthesis, and the special character of inorganic wastes that are really difficult to be degraded but can be easily mobilized in the environment suffering bioaccumulation processes and transformation in the food chain.
Sustainable Nanomaterials
Authors: Ahmad Shahzad , Tripathy Divya Bajpai , Mishra Anuradha
Published: September 2016

Nanotechnology had a major impact in our society, as the diverse nature of nanomaterials shows its necessity in various fields including electronics, energy production, medical, and drug development. Nevertheless, the nanomaterials also show some serious problems on environment, human health and safety upon its exposure either directly or via consumer products. The prime objective of sustainable nanotechnology is to minimize environmental and human health risks associated with the nanomaterials and to encourage replacement of existing materials with new nanomaterials that are more eco‐friendly throughout their lifecycle. Authors briefly discuss on the classification of nanomaterials and their applications.
Ionic Liquids: Industrial Applications
Authors: Durga Geeta , Mishra Anuradha
Published: September 2016

Ionic liquids (ILs) constitute a class of solvents containing organic cation along with organic/inorganic anion characterized by low melting point (<100 °C) and negligible vapor pressure. These solvents are promising alternatives for conventional organic solvents by virtue of being environmentally benign. No toxic gases are released by ILs upon their usage. The physicochemical properties of ILs can easily be tailored by varying the structure/combination of cation and anion ranging from lipophilic to lipophobic, viscous to nonviscous, polar to nonpolar, and water miscible to immiscible. Other desirable properties of ILs are high thermal stability, nonflammability, and large electrochemical window. ILs have been emerged as “green solvents” over the period of time, and the industrial applications of ILs have been increasing progressively, which are diversified from the solvent for the syntheses (organic, inorganic, or polymer) to catalysis, analytical separations, extractions, electrochemistry, lubrication, and so on. Some of the relatively newer industrial applications of ILs are the fabrication of supported liquid membranes (SILM) for the selective separation of different metal ions/organic compounds/biologically important compounds in dilute streams, and gas mixtures, biomass transformation into fuel, and chemicals and nuclear waste management. Many of these have been developing at pilot plant and commercial levels.
Siroheme Decarboxylase in Complex with Iron‐Uroporphyrin
III
Authors: Layer Gunhild
Published: September 2016

Siroheme decarboxylase catalyzes the conversion of siroheme to 12,18‐didecarboxysiroheme during heme
d
1
biosynthesis in denitrifying bacteria and during the alternative heme biosynthesis in archaea and sulfate‐reducing bacteria. The crystal structure of siroheme decarboxylase from
Hydrogenobacter thermophilus
in complex with the substrate analog iron‐uroporphyrin III is available as well as the structure of siroheme decarboxylase from
Desulfovibrio desulfuricans
in complex with the reaction product didecarboxysiroheme. The two structures reveal two possible binding modes for the iron‐containing tetrapyrroles. In both cases, the central iron ion is coordinated by a histidine residue as the axial ligand, however, these histidines are located at different positions of the enzyme. Moreover, although identical amino acid residues coordinate the substrate analog and reaction product, the respective equivalent residues interact with different parts of the respective tetrapyrrole macrocycle. The two observed tetrapyrrole binding modes might hint toward two different binding sites for the initial substrate, siroheme, and the reaction intermediate monodecarboxysiroheme.
Production of Biopropylene Using Biomass‐Derived Sources
Authors: Vasiliadou Efterpi S. , Lemonidou Angeliki A.
Published: September 2016

Propylene along with ethylene forms the backbone of the petrochemical industry. Propylene is the second most important key intermediate for the production of a variety of end‐use chemicals. Industrial processes producing propylene today are primarily steam cracking and fluid catalytic cracking, which amount up to 90% of propylene production. Apart from steam cracking and fluid catalytic cracking, on‐purpose propylene production processes (e.g., dehydrogenation, metathesis, and methanol to olefins) are becoming more important owing to increasing propylene demand. On the other hand, there is intense research interest to sustainable production of propylene using biomass resources instead of fossil raw materials. In this sense, various renewable processes have been developed utilizing lignocellulosic and triglyceride‐based biomass sources. The most important among them are bioethylene and biobutene metathesis as well as biomethanol to propylene. In addition to these technologies, novel catalytic routes based on biomass‐derived oxygenates, the most important being glycerol, have demonstrated high potential for future commercialization. Glycerol‐selective conversion to propylene is realized via catalytic deoxygenation routes at mild operating conditions (200–300 °C). These reactions are catalyzed by either metal catalysts or metal oxide and carbide systems. Molybdenum oxides and carbides have shown unique catalytic performance by selectively activating CO/CO bonds, while retarding CC bonds of the oxygenates. In most cases, propylene is the main product formed achieving very high yields, up to 90%. These processes will definitely play an important role in propylene production in the near future realizing the concept of biorefineries.
Predicting aggression in adolescence: The interrelation between (a lack of) empathy and social goals
Authors: van Hazebroek Babette C. M. , Olthof Tjeert , Goossens Frits A.
Published: September 2016

In an attempt to explain the inconsistent findings and overall weak relation between empathy and aggression, we focused on the role of emotional empathy (emotions of concern, compassion or sympathy toward a (potential) victim), agentic goals (the desire to be dominant during social interaction with peers) and their interplay (mediation or moderation) in the prediction of proactive aggression (learned instrumental behavior) in adolescence. Data were collected from 550 young Dutch adolescents, who filled out multiple questionnaires. Findings showed that the link between a lack of empathic concern and proactive aggression is partly mediated and moderated by agentic goals. The moderation analyses showed that the predictive value of a lack of empathic concern with regard to proactive aggression was greater when adolescents reported a stronger desire to be dominant in social situations with peers. In addition, the findings supported the assumption that the relation between empathic concern and reactive aggression (a hostile and angry response to perceived provocation) is not mediated or moderated by agentic goals. Findings were discussed in terms of their implications for future research. Aggr. Behav. 43:204–214, 2017. © 2016 Wiley Periodicals, Inc.
Gold–Organic Hybrids: On‐Surface Synthesis and Perspectives
Authors: Zhang Haiming , Chi Lifeng
Published: September 2016

Gold–organic hybrids can be prepared on gold substrates by on‐surface dehalogenation of molecular precursors with multiple halogen substituents. Various contact geometries of covalent arylAu bonds are achieved by changing the halogen substituents in the bay or peri regions. Scanning tunneling microscopy/spectroscopy (STM/STS) investigations allow a better understanding of the structure/property relationships in various gold–aryl contacts. Recent progress on the synthesis, large‐scale alignment, and STS measurement of gold–organic hybrids is described, ending with an emphasis on potential future applications, e.g., as precursors (intermediates) for the synthesis of graphene nanoribbons (GNRs) on insulating surfaces, and as a model system to investigate the role of covalent arylAu bonds in electron transport through gold–GNR contacts.
Copper‐Catalyzed Ring‐Expansion/Thiolactonization via Azidation of Internal Olefinic C–H Bond under Mild Conditions
Authors: Guo Tenglong , Jiang Quanbin , Yu Zhengkun
Published: September 2016

A copper(I)‐catalyzed, (diacetoxyiodo)benzene [PhI(OAc)2]‐mediated ring‐expansion/thiolactonization of α‐oxo ketene dithioacetals was efficiently realized via azidation of the internal olefinic C−H bond with sodium azide under mild conditions. Sequential amination, ring‐expansion rearrangement, and thiolactonization occurred to form aminated thiolactones in the presence of acetic anhydride as the additive, while only C−H amination to afford the unprotected enamines occurred when using ammonium sulfide as a reducing additive. The in situ generated vinyl azides were confirmed as the reactive intermediates, which were captured by phenylacetylene to produce triazoles. This protocol provides a concise route to thiolactone derivatives and unprotected enamines.

magnified image
Outcomes of outpatient endoscopic repair of cerebrospinal fluid rhinorrhea
Authors: Adams Austin S. , Francis David O. , Russell Paul T.
Published: September 2016

Background

Endoscopic repair of anterior skull‐base defects has become the gold standard for management of cerebrospinal fluid (CSF) rhinorrhea. Both improved techniques and adjuvant therapies have led to accepted success rates of greater than 90%. As management has evolved, shorter hospitalizations have been required and the goal of this study is to analyze the outcomes of patients repaired on an outpatient basis vs those managed as inpatients postoperatively.

Methods

Patients undergoing endoscopic repair of CSF rhinorrhea between 2004 and 2014 were identified by review of medical records. Demographic and clinical data were collected and compared between patients having surgery with and without postoperative admission. Patients managed with lumbar drains were not included. Statistical analyses were preformed to determine if any differences in patient demographics and outcomes existed.

Results

A total of 86 patients were identified; 39 of 86 patients (45.3%) underwent outpatient surgery; 47 patients were admitted postoperatively with a mean hospital stay of 1.66 days with a median and mode of 1 day. No statistically significant differences were found between leak location, etiology, rates of recurrence, or complications. The outpatient group was found to have a greater proportion of small defects <1 cm2 (p = 0.003). Repair technique was also significantly different between groups (p = 0.001).

Conclusion

Endoscopic management of CSF rhinorrhea is a safe method of treatment with reliable success rates. Our retrospective analysis revealed comparable outcomes in patients treated with and without postoperative hospital admission, and supports the idea that outpatient management may be reasonable in certain patients, especially those with defects <1 cm2.
The Nucleophilicity of Persistent α‐Monofluoromethide Anions
Authors: Zhang Zhe , Puente Ángel , Wang Fang , Rahm Martin , Mei Yuncai , Mayr Herbert , Prakash G. K. Surya
Published: September 2016

α‐Fluorocarbanions are key intermediates in nucleophilic fluoroalkylation reactions. Although frequently discussed, the origin of the fluorine effect on the reactivity of α‐fluorinated CH acids has remained largely unexplored. We have now investigated the kinetics of a series of reactions of α‐substituted carbanions with reference electrophiles to elucidate the effects of α‐F, α‐Cl, and α‐OMe substituents on the nucleophilic reactivities of carbanions.
Cycloaddition von P‐C‐Einfachbindungen: Stereoselektive Bildung von Benzo‐1,3,6,2‐trioxaphosphepinkomplexen über einen ditopischen Van‐der‐Waals‐Komplex
Authors: Malik Payal , Espinosa Ferao Arturo , Schnakenburg Gregor , Streubel Rainer
Published: September 2016

Während für Phosphaalkene und Phosphane die Teilnahme an [4+n]‐Cycloadditionen bekannt ist, sind P‐C‐Einfachbindungen diesbezüglich inert. Wir stellen hier Reaktionen von Oxaphosphirankomplexen mit Tetrachlor‐ortho‐benzochinon (TOB) vor, die eine Reaktion an der endocyclichen P‐C‐Bindung zeigen, welche stereoselektiv zu Benzo‐1,3,6,2‐trioxaphosphepinkomplexen führt. DFT‐Rechnungen auf höchstem Niveau liefern Hinweise darauf, dass das endgültige Produkt aus einer Sequenz dreier konsekutiver Schritte stammt, die einen ditopischen Van‐der‐Waals‐Komplex beinhalten.
Sodium and Manganese Stoichiometry of P2‐Type Na2/3MnO2
Authors: Kumakura Shinichi , Tahara Yoshiyuki , Kubota Kei , Chihara Kuniko , Komaba Shinichi
Published: September 2016

To realize a reversible solid‐state MnIII/IV redox couple in layered oxides, co‐operative Jahn–Teller distortion (CJTD) of six‐coordinate MnIII (t2g3–eg1) is a key factor in terms of structural and physical properties. We develop a single‐phase synthesis route for two polymorphs, namely distorted and undistorted P2‐type Na2/3MnO2 having different Mn stoichiometry, and investigate how the structural and stoichiometric difference influences electrochemical reaction. The distorted Na2/3MnO2 delivers 216 mAh g−1 as a 3 V class positive electrode, reaching 590 Wh (kg oxide)−1 with excellent cycle stability in a non‐aqueous Na cell and demonstrates better electrochemical behavior compared to undistorted Na2/3MnO2. Furthermore, reversible phase transitions correlated with CJTD are found upon (de)sodiation for distorted Na2/3MnO2, providing a new insight into utilization of the MnIII/IV redox couple for positive electrodes of Na‐ion batteries.
Entgiftung von VX und anderen V‐Stoffen in Wasser bei 37 °C und pH 7.4 durch substituierte Sulfonatocalix[4]arene
Authors: Schneider Christian , Bierwisch Anne , Koller Marianne , Worek Franz , Kubik Stefan
Published: September 2016

Sulfonatocalix[4]arene mit einem geeigneten Hydroxamsäurerest können neurotoxische Organophosphonate der Klasse der V‐Stoffe mit Halbwertszeiten bis hinunter zu 3 min in wässriger Pufferlösung bei 37 °C und pH 7.4 entgiften. Diese Aktivität ist auf die millimolare Affinität des Calixarenrings für kationische V‐Stoffe in Kombination mit einer geeigneten Positionierung des Hydroxamsäurerests zurückzuführen. Bei der Reaktion wird zunächst die Hydroxamsäure phosphonyliert. Anschließend erfolgt eine Lossen‐Umlagerung, sodass der Wirkmechanismus dieser Verbindungen insgesamt stöchiometrischer und nicht katalytischer Natur ist. Dennoch stellen die entwickelten Calixarene momentan die effizientesten synthetischen Scavenger dar, die persistente V‐Stoffe unter milden Bedingungen entgiften. Sie können als Leitverbindungen für neue Wirkstoffe aufgefasst werden, die eine Behandlung von Vergiftungen mit hochtoxischen Nervenkampfstoffen ermöglichen.
Detoxification of VX and Other V‐Type Nerve Agents in Water at 37 °C and pH 7.4 by Substituted Sulfonatocalix[4]arenes
Authors: Schneider Christian , Bierwisch Anne , Koller Marianne , Worek Franz , Kubik Stefan
Published: September 2016

Sulfonatocalix[4]arenes with an appended hydroxamic acid residue can detoxify VX and related V‐type neurotoxic organophosphonates with half‐lives down to 3 min in aqueous buffer at 37 °C and pH 7.4. The detoxification activity is attributed to the millimolar affinity of the calixarene moiety for the positively charged organophosphonates in combination with the correct arrangement of the hydroxamic acid group. The reaction involves phosphonylation of the hydroxamic acid followed by a Lossen rearrangement, thus rendering the mode of action stoichiometric rather than catalytic. Nevertheless, these calixarenes are currently the most efficient low‐molecular‐weight compounds for detoxifying persistent V‐type nerve agents under mild conditions. They thus represent lead structures for novel antidotes that allow treatment of poisonings by these highly toxic chemicals.
Deoxyelephantopin induces apoptosis in HepG2 cells via oxidative stress, NF‐κB inhibition and mitochondrial dysfunction
Authors: Mehmood Tahir , Maryam Amara , Zhang He , Li Yongming , Khan Muhammad , Ma Tonghui
Published: September 2016

Deoxyelephantopin (DET), a naturally occurring sesquiterpene lactone present in Chinese medicinal herb, Elephantopus scaber has been shown to exert anti‐inflammatory as well as anticancer effects in various cancer cells of human origin in vitro. However, the exact molecular mechanism underlying DET‐induced apoptosis remains largely unexplored, particularly in human hepatocellular carcinoma G2 (HepG2) cells. In the present study, we found that DET inhibits proliferation and induces apoptosis in HepG2 cells in a dose‐dependent manner. This DET‐mediated apoptosis was found to be associated with reactive oxygen species generation, glutathione depletion and decreased activity of thioredoxin reductase, mitochondrial membrane potential disruption, Bcl‐2 family proteins modulation, cytochrome c release, caspases‐3 activation, PARP cleavage and inhibition of NF‐κB activation. DET inhibited the constitutive as well as induced‐translocation of NF‐κB into nucleus and augmented the apoptotic effect of Gemcitabine. IKK‐16 (NF‐κB inhibitor) further enhanced the cytotoxicity of DET and gemcitabine indicating that DET induces apoptosis in HepG2 cells at least partially through inhibition of NF‐κB activation. Further mechanistic study demonstrated that DET inhibits the translocation of constitutive as well as induced‐NF‐κB into nucleus by decreasing phosphorylation of IкBα. Moreover, pretreatment of cells with 3 mM NAC reversed DET‐mediated cell death and NF‐κB inhibition, indicating that DET exerts its anticancer effects mainly through oxidative stress. Therefore, DET may be developed into a lead chemotherapeutic drug as a single agent or in combination with clinical drugs for the effective treatment of liver cancer. © 2016 BioFactors, 43(1):63–72, 2017
A DNA Circuit for IsomiR Detection
Authors: Connolly Ashley R. , Hirani Rena , Ellis Amanda V. , Trau Matt
Published: September 2016

A synthetic DNA oligonucleotide has been programmed to function as a biological circuit to detect 5′‐IsomiRs. The circuit consists of two integrated DNA switches. The first is “activated” when a DNA probe is enzymatically modified by a reverse transcriptase that incorporates nucleotides complementary to the 5′‐region of a microRNA (miRNA). Addition of the correct number and sequence of nucleotides enables the probe to assemble into an asymmetric DNA hairpin. The reconfigured hairpin probe then primes an internal polymerisation reaction, resulting in the synthesis of a symmetrical DNA hairpin. This activates the second switch, which then initiates the amplification of reverse‐transcribed miRNA through a continuous cycle of DNA nicking and polymerisation. The DNA circuit enables sensitive and rapid detection of femtomoles of a miRNA transcript under isothermal conditions.
Scalable Synthesis of Acidic Mesostructured Silica–Carbon Nanocomposite Catalysts by Rotary Evaporation
Authors: Zhong Ruyi , Peng Li , Iacobescu Remus Ion , Pontikes Yiannis , Shu Riyang , Ma Longlong , Sels Bert F.
Published: September 2016

A practical and scalable synthesis for the mass production of well‐ordered mesoporous silica–carbon composites by using a fast rotary‐evaporation‐induced self‐assembly method in the absence of any additional support is presented.
Solvation Effect Facilitates Ion Transfer across Water/1,2‐Dichloroethane Interface
Authors: Nsabimana Jacques , Nestor Uwitonze , Girma Girum , Pamphile Ndagijimana , Zhan Dongping , Tian Zhong‐Qun
Published: September 2016

Ion transfer across the interface between two immiscible electrolytes can produce a Faraday current involving non‐redox reactions, which is useful for both ion detection and phase‐transfer catalysis. To decrease the transfer energy and improve the selectivity, artificial ligands are needed, which are usually unavailable because of the difficulty in the synthesis. Herein, we demonstrate that the solvation effect can act as the driving force for ion transfer across the micropipette‐supported water/1,2‐dichloroethane interface, including the anions SO42−, NO3−, NO2−, CO32−, and so forth. The thermodynamic properties are discussed, including the diffusion coefficients, Gibbs energy of ion transfer, stoichiometric ratios, and apparent association constants. Meanwhile, the research also provides a method to investigate the solvation effect.
From Ion‐Like Ethylzinc Aluminates to [EtZn(arene)2]+[Al(ORF)4]− Salts
Authors: Petersen Thies Olaf , Simone Dustin , Krossing Ingo
Published: September 2016

Attempts to prepare previously unknown simple and very Lewis acidic [RZn]+[Al(ORF)4]− salts from ZnR2, AlR3, and HO−RF delivered the ion‐like RZn(Al(ORF)4) (R=Me, Et; RF=C(CF3)3) with a coordinated counterion, but never the ionic compound. Increasing the steric bulk in RZn+ to R=CH2CMe3, CH2SiMe3, or Cp*, thus attempting to induce ionization, failed and led only to reaction mixtures including anion decomposition. However, ionization of the ion‐like EtZn(Al(ORF)4) compound with arenes yielded the [EtZn(arene)2]+[Al(ORF)4]− salts with arene=toluene, mesitylene, or o‐difluorobenzene (o‐DFB)/toluene. In contrast to the ion‐like EtZn(η3‐C6H6)(CHB11Cl11), which co‐crystallizes with one benzene molecule, the less coordinating nature of the [Al(ORF)4]− anion allowed the ionization and preparation of the purely organometallic [EtZn(arene)2]+ cation. These stable materials have further applications as, for example, initiators of isobutene polymerization. DFT calculations to compare the Lewis acidities of the zinc cations to those of a large number of organometallic cations were performed on the basis of fluoride ion affinity. The complexation energetics of EtZn+ with arenes and THF was assessed and related to the experiments.
Chemistry and Biology of HPAs: A Family of Ceramide Trafficking Inhibitors
Authors: Berkeš Dušan , Daïch Adam , Santos Cécile , Ballereau Stéphanie , Génisson Yves
Published: September 2016

In 2001, two years before the disclosure of the CERT‐associated Cer transfer machinery, N‐(3‐hydroxy‐1‐hydroxymethyl‐3‐phenylpropyl)alkanamides (HPAs) were described as the first, and to date unique, family of intracellular Cer trafficking inhibitors. The dodecanamide derivative, HPA‐12, turned out to be a benchmark as a cellular inhibitor of CERT‐mediated de novo sphingomyelin biosynthesis. In only 15 years after its first disclosure, this compound has prompted a growing number of biological and chemical studies. Its initial chemical development closely paralleled the study of the CERT protein. It was only after its structural revision in 2011 that HPA‐12 received broad attention from the synthetic chemistry community, leading to novel analogues with enhanced protein binding. This Minireview aims at presenting an exhaustive report of the syntheses of HPA‐12 and analogues. Biological activities of this CERT inhibitor and structure–activity relationships are also presented to afford a comprehensive overview of the chemistry and biology of the HPA series.
Synthesis, Characterization and Unusual Reactivity of Vinylbenziodoxolones—Novel Hypervalent Iodine Reagents
Authors: Stridfeldt Elin , Seemann Alexandra , Bouma Marinus J. , Dey Chandan , Ertan Anne , Olofsson Berit
Published: September 2016

A novel type of hypervalent iodine(III) reagents, vinylbenziodoxolones (VBX), has been synthesized in a one‐pot reaction from 2‐iodobenzoic acid. VBX is bench stable, has been thoroughly characterized and the cyclic structure is supported by X‐ray analysis. The reactivity of VBX was investigated in vinylation of nitrocyclohexane, and delivered vinylated products with opposite regioselectivity compared to acyclic vinyl(aryl)iodonium salts. The reagents could become a powerful tool in vinylation reactions under both metal‐free and metal‐catalyzed conditions.
One‐Pot Halogen Dance/Negishi Coupling of Dibromothiophenes for Regiocontrolled Synthesis of Multiply Arylated Thiophenes
Authors: Okano Kentaro , Sunahara Kazuhiro , Yamane Yoshiki , Hayashi Yuki , Mori Atsunori
Published: September 2016

One‐pot halogen dance/Negishi cross‐coupling of readily available 2,5‐dibromothiophenes is described. A lithium diisopropylamide (LDA)‐mediated halogen dance reaction resulted in the formation of thermodynamically stable α‐lithiodibromothiophenes, which were transmetalated with ZnCl2 and subjected to Negishi cross‐coupling to provide the corresponding arylated dibromothiophenes in one pot. The resultant β‐bromo group was much less reactive than the remaining α‐bromo group, which was used in a one‐pot double Suzuki–Miyaura cross‐coupling, enabling facile synthesis of multiply arylated thiophenes.
Principles and Design of a Zeeman–Sisyphus Decelerator for Molecular Beams
Authors: Fitch N. J. , Tarbutt M. R.
Published: September 2016

We explore a technique for decelerating molecules using a static magnetic field and optical pumping. Molecules travel through a spatially varying magnetic field and are repeatedly pumped into a weak‐field seeking state as they move towards each strong field region, and into a strong‐field seeking state as they move towards weak field. The method is time‐independent and so is suitable for decelerating both pulsed and continuous molecular beams. By using guiding magnets at each weak field region, the beam can be simultaneously guided and decelerated. By tapering the magnetic field strength in the strong field regions, and exploiting the Doppler shift, the velocity distribution can be compressed during deceleration. We develop the principles of this deceleration technique, provide a realistic design, use numerical simulations to evaluate its performance for a beam of CaF, and compare this performance to other deceleration methods.
Excellent Microwave Absorption and Electromagnetic Interference Shielding Based on Reduced Graphene Oxide@MoS2/Poly(Vinylidene Fluoride) Composites
Authors: Guo Ao‐Ping , Zhang Xiao‐Juan , Wang Shan‐Wen , Zhu Jia‐Qiang , Yang Lin , Wang Guang‐Sheng
Published: September 2016

Reduced graphene oxide (rGO)@MoS2 composites with a loose structure were prepared and added to poly(vinylidene fluoride) (PVDF) to form composites that showed superior microwave absorption and excellent electromagnetic interference shielding performances. The maximum reflection loss of the rGO@MoS2/PVDF composites, with a low filling rate (only 5.0 wt %), can reach −43.1 dB at 14.48 GHz, and the frequency bandwidth below −10 dB is 3.6–17.8 GHz (in the frequency range of 2–18 GHz) with a thickness of 1–5 mm. Furthermore, rGO@MoS2/PVDF composites with a higher filling rate (25 wt %) also exhibit outstanding electromagnetic interference shielding effectiveness, reaching a maximum at 27.9 dB. The mechanism of enhanced absorption and electromagnetic interference shielding performances were also studied in detail.
Sampled‐data reliable stabilization of T‐S fuzzy systems and its application
Authors: Sakthivel Rathinasamy , Boomipalagan Kaviarasan , Yong‐Ki MA , Muslim Malik
Published: September 2016

In this article, based on sampled‐data approach, a new robust state feedback reliable controller design for a class of Takagi–Sugeno fuzzy systems is presented. Different from the existing fault models for reliable controller, a novel generalized actuator fault model is proposed. In particular, the implemented fault model consists of both linear and nonlinear components. Consequently, by employing input‐delay approach, the sampled‐data system is equivalently transformed into a continuous‐time system with a variable time delay. The main objective is to design a suitable reliable sampled‐data state feedback controller guaranteeing the asymptotic stability of the resulting closed‐loop fuzzy system. For this purpose, using Lyapunov stability theory together with Wirtinger‐based double integral inequality, some new delay‐dependent stabilization conditions in terms of linear matrix inequalities are established to determine the underlying system's stability and to achieve the desired control performance. Finally, to show the advantages and effectiveness of the developed control method, numerical simulations are carried out on two practical models. © 2016 Wiley Periodicals, Inc. Complexity 21: 518–529, 2016
Enhanced Adsorption Efficiency through Materials Design for Direct Air Capture over Supported Polyethylenimine
Authors: Sayari Abdelhamid , Liu Qing , Mishra Prashant
Published: September 2016

Until recently, carbon capture and sequestration (CCS) was regarded as the most promising technology to address the alarming increase in the concentration of anthropogenic CO2 in the atmosphere. There is now an increasing interest in carbon capture and utilization (CCU). In this context, the capture of CO2 from air is an ideal solution to supply pure CO2 wherever it is needed. Here, we describe innovative materials for direct air capture (DAC) with unprecedented efficiency. Polyethylenimine (PEI) was supported on PME, which is an extra‐large‐pore silica (pore‐expanded MCM‐41) with its internal surfaces fully covered by a uniform layer of readily accessible C16 chains from cetyltrimethylammonium (CTMA+) cations. The CTMA+ layer plays a key role in enhancing the amine efficiency toward dry or humid ultradilute CO2 (400 ppm CO2/N2) to unprecedented levels. At the same PEI content, the amine efficiency of PEI/PME was two to four times higher than that of the corresponding calcined mesoporous silica loaded with PEI or with different combinations of C16 chains and PEI. Under humid conditions, the amine efficiency of 40 wt % PEI/PME reached 7.31 mmol
/gPEI, the highest ever reported for any supported PEI in the presence of 400 ppm CO2. Thus, amine accessibility, which reflects both the state of PEI dispersion and the adsorption efficiency, is intimately associated with the molecular design of the adsorbent.
100 °C Thermal Stability of Printable Perovskite Solar Cells Using Porous Carbon Counter Electrodes
Authors: Baranwal Ajay K. , Kanaya Shusaku , Peiris T. A. Nirmal , Mizuta Gai , Nishina Tomoya , Kanda Hiroyuki , Miyasaka Tsutomu , Segawa Hiroshi , Ito Seigo
Published: September 2016

Many efforts have been made towards improving perovskite (PVK) solar cell stability, but their thermal stability, particularly at 85 °C (IEC 61646 climate chamber tests), remains a challenge. Outdoors, the installed solar cell temperature can reach up to 85 °C, especially in desert regions, providing sufficient motivation to study the effect of temperature stress at or above this temperature (e.g., 100 °C) to confirm the commercial viability of PVK solar cells for industrial companies. In this work, a three‐layer printable HTM‐free CH3NH3PbI3 PVK solar cell with a mesoporous carbon back contact and UV‐curable sealant was fabricated and tested for thermal stability over 1500 h at 100 °C. Interestingly, the position of the UV‐curing glue was found to drastically affect the device stability. The side‐sealed cells show high PCE stability and represent a large step toward commercialization of next generation organic–inorganic lead halide PVK solar cells.
Graphene–Perovskite Solar Cells Exceed 18 % Efficiency: A Stability Study
Authors: Agresti Antonio , Pescetelli Sara , Taheri Babak , Del Rio Castillo Antonio Esaù , Cinà Lucio , Bonaccorso Francesco , Di Carlo Aldo
Published: September 2016

Interface engineering is performed by the addition of graphene and related 2 D materials (GRMs) into perovskite solar cells (PSCs), leading to improvements in the power conversion efficiency (PCE). By doping the mesoporous TiO2 layer with graphene flakes (mTiO2+G), produced by liquid‐phase exfoliation of pristine graphite, and by inserting graphene oxide (GO) as an interlayer between the perovskite and hole‐transport layers, using a two‐step deposition procedure in air, we achieved a PCE of 18.2 %. The obtained PCE value mainly results from improved charge‐carrier injection/collection with respect to conventional PSCs. Although the addition of GRMs does not influence the shelf life, it is beneficial for the stability of PSCs under several aging conditions. In particular, mTiO2+G PSCs retain more than 88 % of the initial PCE after 16 h of prolonged 1 sun illumination at the maximum power point. Moreover, when subjected to prolonged heating at 60 °C, the GO‐based structures show enhanced stability with respect to mTiO2+G PSCs, as a result of thermally induced modification at the mTiO2+G/perovskite interface. The exploitation of GRMs in the form of dispersions and inks opens the way for scalable large‐area production, advancing the possible commercialization of PSCs.
Encapsulation of Perovskite Solar Cells for High Humidity Conditions
Authors: Dong Qi , Liu Fangzhou , Wong Man Kwong , Tam Ho Won , Djurišić Aleksandra B. , Ng Annie , Surya Charles , Chan Wai Kin , Ng Alan Man Ching
Published: September 2016

Invited for this month′s cover is the group of Aleksandra B. Djurišić at the University of Hong Kong along with collaborators from the University of Hong Kong, Hong Kong Polytechnic University, and South University of Science & Technology of China. The image shows outdoor testing performance of perovskite solar cells during summer in Hong Kong. The Full Paper itself is available at 10.1002/cssc.201600868.
Metastatic Signet‐Ring Cell Carcinoma of the Bladder in Cerebrospinal Fluid
Authors: Lin Diana Murro , Park Ji‐Weon , Gattuso Paolo
Published: September 2016

Primary bladder signet‐ring cell carcinoma (SRCC) is extremely rare and associated with an aggressive course. To our knowledge, we describe the first metastatic bladder SRCC identified in cerebrospinal fluid (CSF). A 68‐year‐old male with 1 year history of primary bladder SRCC with spinal metastasis presented with multiple falls and loss of consciousness. Brain imaging showed high signal in the frontoparietal sulci and superior cerebellum. CSF analysis was significant for increased leukocytes with monocyte predominance while protein and glucose values were within normal range. There was a hypercellular population of pleomorphic tumor cells with signet‐ring morphology, similar to those seen in his diagnostic bladder biopsies. The signet‐ring cells were positive for cytokeratin 7 and 20 and negative for CDX‐2 and prostate‐specific antigen. The patient's clinical condition rapidly deteriorated and he died less than a week after presentation. At autopsy, brain sections revealed signet ring cells in the meninges overlying the cerebrum, cerebellum, brainstem, spinal cord, and pituitary with superficial invasion of the brain parenchyma. No brain parenchymal lesions were present. This case illustrates a unique complication of primary bladder SRCC. Diagn. Cytopathol. 2017;45:73–76. © 2016 Wiley Periodicals, Inc.
Create a process to handle requests for emotional support assistance animals in campus housing
Authors: Masinter Michael R.
Published: September 2016

The July 2016 American Bar Association Journal published an article reporting a significant increase in students requesting authorization to keep an emotional support assistance animal in campus housing. The Fair Housing Act obligates schools to consider such requests when an ESA is necessary to provide equal use and enjoyment of housing. Because ESAs are not service animals, and because the Americans with Disabilities Act regulates only the rights of individuals with service animals, the ADA service animal regulations, including the familiar two‐question rule, do not apply to student requests to keep ESAs in university housing.
Synthesis of Spherical ZnO Microcrystals by Laser Ablation in Air
Authors: NAKAMURA DAISUKE , TANAKA TOSHINOBU , IKEBUCHI TATSUYA , UEYAMA TAKESHI , HIGASHIHATA MITSUHIRO , OKADA TATSUO
Published: September 2016

We have succeeded in synthesizing the zinc oxide (ZnO) microspheres by laser ablation of a ZnO sintered target in air, and have demonstrated ultraviolet whispering‐gallery‐mode lasting from the sphere under ultraviolet pulsed laser excitation. In this study, we investigated the dependence of the laser fluence and the spot size on the growth of the ZnO microspheres. Large sizes of more than 30 μm microspheres were synthesized with increasing the laser fluence up to 440 J/cm2. Although undesired nanoparticles and fragments were also generated at high fluence and large ablation spot size, selective collection of the microspheres can be expected because of different emitting distributions of the microspheres and other fragments.
Preparation of Gold Submicron‐Sized Particles Using Laser Irradiation for Gold Nanoparticles Stabilized by Carbonate
Authors: TSUJI TAKESHI , TAKADE ISAMI , TSUJI MASAHARU , ISHIKAWA YOSHIE , KOSHIZAKI NAOTO
Published: September 2016

Laser irradiation for colloidal gold nanoparticles stabilized by Na2CO3 was carried out to prepare submicron‐sized spherical particles of gold. The source gold nanoparticles stabilized by Na2CO3 (CO32−) were prepared using laser ablation in an aqueous solutions containing Na2CO3 and then nonfocused laser irradiation for the source nanoparticles was carried out to induce the agglomeration and fusion of the nanoparticles. Similarly to the case using the source nanoparticles stabilized by citrate, submicron particles were obtained. It was found that the formation process and size of the submicron particles strongly depend on the stabilizing reagents.
Large‐Volume Data Compression Using Compressed Sensing for Meteorological Radar
Authors: SHIMAMURA SHIGEHARU , KIKUCHI HIROSHI , MATSUDA TAKAHIRO , KIM GWAN , YOSHIKAWA EIICHI , NAKAMURA YOSHITAKA , USHIO TOMOO
Published: September 2016

In Japan, severe weather phenomena such as heavy rains and tornados sometimes cause meteorological disasters. In many cases, these are micro scale phenomena in the sense of spatial and temporal resolutions, which make it difficult to detect them with conventional meteorological radars due to their insufficient spatial and temporal resolutions. Therefore, we have been developing meteorological radars with high resolution and accuracy such as phased array radar (PAR) and Ku‐band broad band radar (BBR), and radar network systems consisting of multiple PARs and BBRs to realize further enhancement of the radar performance in terms of efficiency and accuracy. These high‐resolution radars, however, definitely produce large‐volume data, which is unacceptable in a current backbone information network. In order to solve this problem, in this paper, we tackle the compression of the large‐volume radar data by using Compressed sensing (CS), which can realize highly efficient data compression for sparse signals. When using CS, the radar data are compressed by projecting it onto a randomly generated subspace, and the compressed data are reconstructed by solving a simple ℓ1 optimization problem. We apply the CS‐based data compression scheme to measured radar reflectivity factor, and evaluate the relation between compression ratio and reconstruction accuracy. For the compression ratio of 0.3, rainfall rate calculated from the reconstructed radar reflectivity factor has a mean error of ‐0.89 mm/h with more than 30 dBZ precipitation.
Community trait structure in phytoplankton: seasonal dynamics from a method for sparse trait data
Authors: Edwards Kyle F.
Published: September 2016

The distribution of functional traits in communities, and how trait distributions shift over time and space, is critical information for understanding community structure, the maintenance of diversity, and community effects on ecosystem function. It is often the case that traits tightly linked to ecological performance, such as physiological capacities, are laborious to measure and largely unknown for speciose communities; however, these traits are particularly important for unraveling the mechanistic basis of community structure. Here I develop a method combining sparse trait data with a statistical niche model to infer trait distributions for phytoplankton communities and how they vary over 10 yr in the western English Channel. I find that community‐average nitrate affinity, light‐limited growth rate, and maximum growth rate all show major seasonal patterns, reflecting alternate limitation by light vs. nitrogen. Trait diversity exhibits a variety of patterns distinct from community trait means, which suggests complex regulation of functional diversity. Patterns such as these are important for predicting how ocean ecosystems will respond to global change, and for developing trait‐based models of emergent community structure. The statistical approach used here could be applied to any kind of organism, if it exhibits strong relationships between traits and statistical niche estimates.
Solution Conformation and Self‐Assembly of Ferrocenyl(thio)ureas
Authors: Hanauer Kristina , Pham Minh Thu , Förster Christoph , Heinze Katja
Published: September 2016

Conformations and (dis)assembly processes of ureas and thioureas are of fundamental importance in supramolecular chemistry, anion binding, or crystal engineering, both in solution and in the solid state. For sensing and switching processes a redox‐active unit, such as the ferrocene/ferrocenium couple, is especially suitable. Here, self‐assembly processes of redox‐active ferrocenyl(thio)ureas FcNHC(X)NHR [X = O, R = Fc (1), Ph (2), 1‐naphthyl (3), Me (4), Et (5); X = S, R = Fc (6), 1‐anthracenyl (7)] through hydrogen bonds – both in the solid state and in THF and CH2Cl2 solution – are reported. Special emphasis is placed on the impact of nonclassical intramolecular NH···Fe hydrogen bonds in these organometallic systems [these are absent in conventional organic (thio)ureas] on conformation and assembly. Furthermore, conformational switching and disassembly of 1–6 is induced by oxidation of 1–6 to the corresponding ferrocenium cations 1+–6+ (redox switch).
Imines in the Titanium Coordination Sphere: η1‐Imine Complexes as Sources of Azavinylidenes and Four‐Membered Imine–Amido‐N,N′ Chelates
Authors: Loose Florian , Schmidtmann Marc , Saak Wolfgang , Beckhaus Rüdiger
Published: September 2016

In titanium imine complexes the ligand can exhibit several bonding modes. While η2‐imine complexes are intermediates in several catalytic transformations and well investigated, the potential of imines to coordinate through the lone pair of electrons of the nitrogen atom by a dative bond to the titanium center is studied herein. The formation of several bis‐η1 complexes by the reaction of Schiff bases with titanium(IV) chloride was observed. Depending on the substitution pattern of the imine, also complexes with 1:1 stoichiometry are formed. Particular attention is paid to the reaction of imines bearing an SiMe3 group at the nitrogen atom. Titanium complexes of such imines open access to a remarkable N,N′‐bidentate ligand system (4), which can only be obtained in the coordination sphere of the metal atom and cannot be formed by conventional organic synthesis. In this context, imines 2d and 2i were also treated with [CpTiCl3] to yield titanaazavinylidenes 6a and 6b, which may be useful for further modifications.
Microwave‐Assisted Construction of Pyrrolopyridinone Ring Systems by Using an Ugi/Indole Cyclization Reaction
Authors: Li Yong , Lei Jie , Chen Zhong‐Zhu , Tang Dian‐Yong , Yuan Huan , Wang Miao , Zhu Jin , Xu Zhi‐Gang
Published: September 2016

A series of pyrrolopyridinones were prepared by using N‐Boc‐pyrrole‐2‐carbaldehyde as a starting material in an Ugi reaction followed by an acid‐mediated indole cyclization to result in the formation of a new C–C bond. Changes to the other starting materials in this Ugi/indole cyclization reaction sequence extended the scope of this method to include a nucleophilic substitution reaction and an Ugi/deprotection/cyclization (UDC) strategy, which provided access to two new series of heterocyclic compounds. This method represents a facile and efficient one‐pot procedure for the preparation of pyrrolopyridinones under acidic conditions.
Manganese‐Promoted Oxidative Cyclization of Unsaturated Oximes Using Molecular Oxygen in Air under Ambient Conditions
Authors: Yamamoto Daisuke , Oguro Takuto , Tashiro Yuuki , Soga Masayuki , Miyashita Kazuhito , Aso Yoshiaki , Makino Kazuishi
Published: September 2016

A highly efficient manganese‐promoted oxidative cyclization of unsaturated oximes to afford the corresponding 4,5‐dihydroisoxazoline alcohols was developed. A very low loading (generally 0.1–0.2 mol‐%) of Mn(acac)3 (acac = acetylacetonate) promoted the oxidative cyclization through the direct incorporation of molecular oxygen present in air (open flask) at room temperature.
Optimization of Cold Storage Efficiency in a Rankine‐Cycle‐Based Cold Energy Storage System
Authors: Du Yanping , Ding Yulong
Published: September 2016

A 5 kW small‐scale cold energy storage (CES) system based on subcritical CO2 was studied by thermodynamic analysis. If off‐peak electricity is used to heat CO2 in the superheater, the predicted storage efficiency is 30–40 % if we consider the actual efficiencies of the key components in the CES system. In the ideal case, the maximum storage efficiency is as high as 43.9 %. The value of the storage efficiency is much larger and can be over 100 % if waste heat is utilized in the heater. The parametric study showed that the cold storage efficiency in the CES system was improved with an increase of the operating pressure and component efficiencies. The mass flow rate of CO2 and the temperature at the inlet of the engine had a negative contribution to the storage efficiency because of the increased electricity consumption in the superheater.
Detoxification of a triphenylmethane textile colorant using acclimated cells of Bacillus mannanilyticus strain AVS
Authors: Anil Kumar Madhava , Kamalraj Harthy Durai , Vinoth Kumar Vaidyanathan , Gowthami Balashri Kaliamurthy , Seenuvasan Muthulingam , Anuradha Dhanasekaran , Sivanesan Subramanian
Published: September 2016

An indigenous bacterium, Bacillus mannanilyticus strain AVS from an acclimated mixed bacterial culture was screened to biotransform a triphenylmethane dye; methyl violet (MV). The strain was acclimated to MV structure and thus, the cells exhibited an average decolorization rate (ADR) of 69.44 μg min−1 with simultaneous reduction in chemical oxygen demand (COD) level (94%) when incubated for 24 h under static condition. The inducible extracellular oxidoreductases catalyzed MV biotransformation and produced metabolites which were devoid of chlorine. The phytotoxicity assays assessed the toxicity of the biotransformed products. This is the first report on TPM dye degradation and mineralization using B. mannanilyticus strain AVS. © 2016 American Institute of Chemical Engineers Environ Prog, 36: 394–403, 2017