bluuebunny/crossref_metadata_2025 huggingface dataset:
Simulated responses of terrestrial aridity to black carbon and sulfate aerosols
Authors: Lin L. , Gettelman A. , Xu Y. , Fu Q.
Published: January 2016

Aridity index (AI), defined as the ratio of precipitation to potential evapotranspiration (PET), is a measure of the dryness of terrestrial climate. Global climate models generally project future decreases of AI (drying) associated with global warming scenarios driven by increasing greenhouse gas and declining aerosols. Given their different effects in the climate system, scattering and absorbing aerosols may affect AI differently. Here we explore the terrestrial aridity responses to anthropogenic black carbon (BC) and sulfate (SO4) aerosols with Community Earth System Model simulations. Positive BC radiative forcing decreases precipitation averaged over global land at a rate of 0.9%/°C of global mean surface temperature increase (moderate drying), while BC radiative forcing increases PET by 1.0%/°C (also drying). BC leads to a global decrease of 1.9%/°C in AI (drying). SO4 forcing is negative and causes precipitation a decrease at a rate of 6.7%/°C cooling (strong drying). PET also decreases in response to SO4 aerosol cooling by 6.3%/°C cooling (contributing to moistening). Thus, SO4 cooling leads to a small decrease in AI (drying) by 0.4%/°C cooling. Despite the opposite effects on global mean temperature, BC and SO4 both contribute to the twentieth century drying (AI decrease). Sensitivity test indicates that surface temperature and surface available energy changes dominate BC‐ and SO4‐induced PET changes.
CSF Aβ42/Aβ40 and Aβ42/Aβ38 ratios: better diagnostic markers of Alzheimer disease
Authors: Janelidze Shorena , Zetterberg Henrik , Mattsson Niklas , Palmqvist Sebastian , Vanderstichele Hugo , Lindberg Olof , van Westen Danielle , Stomrud Erik , Minthon Lennart , Blennow Kaj ,   the Swedish BioFINDER study group, Hansson Oskar
Published: January 2016

Objective

The diagnostic accuracy of cerebrospinal fluid (CSF) biomarkers for Alzheimer's disease (AD) must be improved before widespread clinical use. This study aimed to determine whether CSF Aβ42/Aβ40 and Aβ42/Aβ38 ratios are better diagnostic biomarkers of AD during both predementia and dementia stages in comparison to CSF Aβ42 alone.

Methods

The study comprised three different cohorts (n = 1182) in whom CSF levels of Aβ42, Aβ40, and Aβ38 were assessed. CSF Aβs were quantified using three different immunoassays (Euroimmun, Meso Scale Discovery, Quanterix). As reference standard, we used either amyloid (18F‐flutemetamol) positron emission tomography (PET) imaging (n = 215) or clinical diagnosis (n = 967) of well‐characterized patients.

Results

When using three different immunoassays in cases with subjective cognitive decline and mild cognitive impairment, the CSF Aβ42/Aβ40 and Aβ42/Aβ38 ratios were significantly better predictors of abnormal amyloid PET than CSF Aβ42. Lower Aβ42, Aβ42/Aβ40, and Aβ42/Aβ38 ratios, but not Aβ40 and Aβ38, correlated with smaller hippocampal volumes measured by magnetic resonance imaging. However, lower Aβ38, Aβ40, and Aβ42, but not the ratios, correlated with non‐AD‐specific subcortical changes, that is, larger lateral ventricles and white matter lesions. Further, the Aβ42/Aβ40 and Aβ42/Aβ38 ratios showed increased accuracy compared to Aβ42 when distinguishing AD from dementia with Lewy bodies or Parkinson's disease dementia and subcortical vascular dementia, where all Aβs (including Aβ42) were decreased.

Interpretation

The CSF Aβ42/Aβ40 and Aβ42/Aβ38 ratios are significantly better than CSF Aβ42 to detect brain amyloid deposition in prodromal AD and to differentiate AD dementia from non‐AD dementias. The ratios reflect AD‐type pathology better, whereas decline in CSF Aβ42 is also associated with non‐AD subcortical pathologies. These findings strongly suggest that the ratios rather than CSF Aβ42 should be used in the clinical work‐up of AD.
Browsing the Real World using Organic Electronics, Si‐Chips, and a Human Touch
Authors: Berggren Magnus , Simon Daniel T. , Nilsson David , Dyreklev Peter , Norberg Petronella , Nordlinder Staffan , Ersman Peter Andersson , Gustafsson Göran , Wikner J. Jacob , Hederén Jan , Hentzell Hans
Published: January 2016

Organic electronics have been developed according to an orthodox doctrine advocating “all‐printed’’, “all‐organic’’ and “ultra‐low‐cost’’ primarily targeting various e‐paper applications. In order to harvest from the great opportunities afforded with organic electronics potentially operating as communication and sensor outposts within existing and future complex communication infrastructures, high‐quality computing and communication protocols must be integrated with the organic electronics. Here, we debate and scrutinize the twinning of the signal‐processing capability of traditional integrated silicon chips with organic electronics and sensors, and to use our body as a natural local network with our bare hand as the browser of the physical world. The resulting platform provides a body network, i.e., a personalized web, composed of e‐label sensors, bioelectronics, and mobile devices that together make it possible to monitor and record both our ambience and health‐status parameters, supported by the ubiquitous mobile network and the resources of the “cloud”.
Extending DNA‐Based Molecular Photonic Wires with Homogeneous Förster Resonance Energy Transfer
Authors: Díaz Sebastián A. , Buckhout‐White Susan , Ancona Mario G. , Spillmann Christopher M. , Goldman Ellen R. , Melinger Joseph S. , Medintz Igor L.
Published: January 2016

Molecular photonic wires (MPWs) precisely position dyes using structural DNA methodologies where they exploit Förster resonance energy transfer (FRET) to direct photonic energy over nm distances with potential applications in light harvesting, biosensing, and molecular electronics. Although versatile, the number of donor–acceptor dye pairs available and the downhill nature of FRET combine to limit the size and efficiency of current MPWs. HomoFRET between identical dyes should provide zero energy loss but at the cost of random transfer directionality. Here, it has been investigated what HomoFRET has to offer as a means to extend MPWs. Steady‐state‐, lifetime‐, and fluorescence anisotropy measurements along with mathematical models are utilized to experimentally examine various 3‐, 4‐, and 5‐dye MPW constructs containing from 1 to 6 HomoFRET repeat sections. Results show that HomoFRET can be extended up to 6 repeat dyes/5 steps with only a ≈55% energy transfer efficiency decrease while doubling the longest MPW length to a remarkable 30 nm. Critically, analogous constructs lacking the HomoFRET portion are unable to deliver any energy over the same lengths. Even with nondirectionality, the introduction of a repeated‐optimized HomoFRET transfer dye is preferable compared to additional less efficient dye species. HomoFRET further provides the benefit of having a higher energy output.
Efficient adsorptive desulfurization by task‐specific porous organic polymers
Authors: Jin Tian , An Shuhao , Yang Xuejing , Hu Jun , Wang Hualin , Liu Honglai , Tian Ziqi , Jiang De‐en , Mehio Nada , Zhu Xiang
Published: January 2016

A task‐specific mesoporous organic polymer (TSPOP) with unique features like good porosity and rich aromatic phenyl groups was facilely made and utilized as a promising adsorptive desulfurization absorbent for the first time. The material exhibits an efficient saturated adsorption of dibenzothiophene (DBT), as high as 111.1 mg g−1. In addition, the intrinsic mesoporous skeleton of TSPOP gave rise to a facile incorporation of uniform Ag(I) species inside the network which facilitated the uptake of organosulfur compounds. A significantly higher saturated DBT adsorption for Ag(I)‐loaded TSPOP reaches 203.7 mg g−1 via a multiple‐site interaction. A detailed model study based on the density functional calculation provides a deeper understanding of the origin of this high activity. In addition to the π–π stacking between DBT and phenyl rings, there exists an additional π‐complexation adsorption with Ag(I) ions, thus, significantly improving the DBT capture performance. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1740–1746, 2016
A Semi‐Conductive Copper–Organic Framework with Two Types of Photocatalytic Activity
Authors: Wu Zhi‐Lei , Wang Chang‐Hong , Zhao Bin , Dong Jie , Lu Feng , Wang Wei‐Hua , Wang Wei‐Chao , Wu Guang‐Jun , Cui Jian‐Zhong , Cheng Peng
Published: January 2016

Based on the newly designed ligand 4′‐(3,5‐dicarboxyphenyl)‐4,2′:6′,4′′‐terpyridine (DCTP), a unique semi‐conductive 3D framework {[CuΙCuΙΙ2(DCTP)2]NO3⋅1.5 DMF}n (1) with a narrow band gap of 2.1 eV, was obtained and structurally characterized. DFT calculations with van de Waals correction employed to explore the electronic structure of 1, clearly revealed its semi‐conductive behavior. Furthermore, we found that 1 exhibits a superior band alignment with water to produce hydrogen and degrade organic pollutants. Without adding any photosensitizers, 1 displays an efficiently photocatalytic hydrogen production in water based on the photo‐generated electrons under UV/Vis light. 1 also exhibits excellent photo‐degradation of methyl blue under visible‐light owing to the strong oxidization of excited holes. It is the first example of MOFs with doubly photocatalytic activities related to photo‐generated electrons and holes, respectively.
In Situ Observation of Successive Crystallizations and Metastable Intermediates in the Formation of Metal–Organic Frameworks
Authors: Yeung Hamish H.‐M. , Wu Yue , Henke Sebastian , Cheetham Anthony K. , O'Hare Dermot , Walton Richard I.
Published: January 2016

Understanding the driving forces controlling crystallization is essential for the efficient synthesis and design of new materials, particularly metal–organic frameworks (MOFs), where mild solvothermal synthesis often allows access to various phases from the same reagents. Using high‐energy in situ synchrotron X‐ray powder diffraction, we monitor the crystallization of lithium tartrate MOFs, observing the successive crystallization and dissolution of three competing phases in one reaction. By determining rate constants and activation energies, we fully quantify the reaction energy landscape, gaining important predictive power for the choice of reaction conditions. Different reaction rates are explained by the structural relationships between the products and the reactants; larger changes in conformation result in higher activation energies. The methods we demonstrate can easily be applied to other materials, opening the door to a greater understanding of crystallization in general.
Electronic Structure of Copper Corroles
Authors: Lemon Christopher M. , Huynh Michael , Maher Andrew G. , Anderson Bryce L. , Bloch Eric D. , Powers David C. , Nocera Daniel G.
Published: January 2016

The ground state electronic structure of copper corroles has been a topic of debate and revision since the advent of corrole chemistry. Computational studies formulate neutral Cu corroles with an antiferromagnetically coupled CuII corrole radical cation ground state. X‐ray photoelectron spectroscopy, EPR, and magnetometry support this assignment. For comparison, CuII isocorrole and [TBA][Cu(CF3)4] were studied as authentic CuII and CuIII samples, respectively. In addition, the one‐electron reduction and one‐electron oxidation processes are both ligand‐based, demonstrating that the CuII centre is retained in these derivatives. These observations underscore ligand non‐innocence in copper corrole complexes.
Konformativer Schlupf bestimmt die Rotationsfrequenz in Fünf‐Komponenten‐Nanorotoren
Authors: Samanta Soumen K. , Rana Anup , Schmittel Michael
Published: January 2016

Mehrere Fünf‐Komponenten‐Nanorotoren ROT‐3 mit unterschiedlicher Geschwindigkeit wurden durch Zugabe von als Bremsklötzen dienenden Phenanthrolin‐Bausteinen unterschiedlicher lateraler Ausdehnung aus dem Vier‐Komponenten‐Nanorotor ROT‐2 hergestellt. Die Bremsklötze interferieren mit dem 180°‐Rotor und führen zu einer Absenkung der Rotationsfrequenz von 97 auf 5 kHz. Die Auswirkung der ebenfalls rotierenden Bremsklötze auf die Rotationsfrequenz in ROT‐3 wird durch das nanomechanische Modell “konformativer Schlupf” präzise vorausgesagt. Für die Quantifizierung wird die Wechselwirkung der Bremsklötze mit der Trajektorie des Hauptrotators evaluiert, wozu die Zahl der interferierenden und der nichtinterferierenden Konformationen mit PM6 berechnet wird.
Intermolecular Electronic Coupling of Organic Units for Efficient Persistent Room‐Temperature Phosphorescence
Authors: Yang Zhiyong , Mao Zhu , Zhang Xuepeng , Ou Depei , Mu Yingxiao , Zhang Yi , Zhao Cunyuan , Liu Siwei , Chi Zhenguo , Xu Jiarui , Wu Yuan‐Chun , Lu Po‐Yen , Lien Alan , Bryce Martin R.
Published: January 2016

Although persistent room‐temperature phosphorescence (RTP) emission has been observed for a few pure crystalline organic molecules, there is no consistent mechanism and no universal design strategy for organic persistent RTP (pRTP) materials. A new mechanism for pRTP is presented, based on combining the advantages of different excited‐state configurations in coupled intermolecular units, which may be applicable to a wide range of organic molecules. By following this mechanism, we have developed a successful design strategy to obtain bright pRTP by utilizing a heavy halogen atom to further increase the intersystem crossing rate of the coupled units. RTP with a remarkably long lifetime of 0.28 s and a very high quantum efficiency of 5 % was thus obtained under ambient conditions. This strategy represents an important step in the understanding of organic pRTP emission.
The [B3(NN)3]+ and [B3(CO)3]+ Complexes Featuring the Smallest π‐Aromatic Species B3+
Authors: Jin Jiaye , Wang Guanjun , Zhou Mingfei , Andrada Diego M. , Hermann Markus , Frenking Gernot
Published: January 2016

We report the spectroscopic identification of the [B3(NN)3]+ and [B3(CO)3]+ complexes, which feature the smallest π‐aromatic system B3+. A quantum chemical bonding analysis shows that the adducts are mainly stabilized by L→[B3L2]+ σ‐donation.
End‐to‐End Self‐Assembly of Semiconductor Nanorods in Water by Using an Amphiphilic Surface Design
Authors: Taniguchi Yuki , Takishita Takao , Kawai Tsuyoshi , Nakashima Takuya
Published: January 2016

One‐dimensional (1D) self‐assemblies of nanocrystals are of interest because of their vectorial and polymer‐like dynamic properties. Herein, we report a simple method to prepare elongated assemblies of semiconductor nanorods (NRs) through end‐to‐end self‐assembly. Short‐chained water‐soluble thiols were employed as surface ligands for CdSe NRs having a wurtzite crystal structure. The site‐specific capping of NRs with these ligands rendered the surface of the NRs amphiphilic. The amphiphilic CdSe NRs self‐assembled to form elongated wires by end‐to‐end attachment driven by the hydrophobic effect operating between uncapped NR ends. The end‐to‐end assembly technique was further applied to CdS NRs and CdSe tetrapods (TPs) with a wurtzite structure.
Formation of α‐SF5‐Enolate Enables Preparation of 3‐SF5‐Quinolin‐2‐ones, 3‐SF5‐Quinolines, and 3‐SF5‐Pyridin‐2‐ones: Evaluation of their Physicochemical Properties
Authors: Joliton Adrien , Plancher Jean‐Marc , Carreira Erick M.
Published: January 2016

This study describes, for the first time, the generation of a SF5‐substituted ester enolate from benzyl SF5‐acetate under soft enolization conditions, which in turn participates in aldol addition reactions in high yield. The reaction was applied in the synthesis of 3‐SF5‐quinolin‐2‐ones, 3‐SF5‐quinolines, and 3‐SF5‐pyridin‐2‐ones, none of which have previously been reported. To provide guidelines for their use in drug discovery, the physicochemical properties of these building blocks were determined and compared with those of their CF3‐ and t‐Bu‐analogues.
Tailored Synthesis of Octopus‐type Janus Nanoparticles for Synergistic Actively‐Targeted and Chemo‐Photothermal Therapy
Authors: Zhang Lingyu , Chen Yinyin , Li Zilu , Li Lu , Saint‐Cricq Philippe , Li Chunxia , Lin Jun , Wang Chungang , Su Zhongmin , Zink Jeffrey I.
Published: January 2016

A facile, reproducible, and scalable method was explored to construct uniform Au@poly(acrylic acid) (PAA) Janus nanoparticles (JNPs). The as‐prepared JNPs were used as templates to preferentially grow a mesoporous silica (mSiO2) shell and Au branches separately modified with methoxy‐poly(ethylene glycol)‐thiol (PEG) to improve their stability, and lactobionic acid (LA) for tumor‐specific targeting. The obtained octopus‐type PEG‐Au‐PAA/mSiO2‐LA Janus NPs (PEG‐OJNP‐LA) possess pH and NIR dual‐responsive release properties. Moreover, DOX‐loaded PEG‐OJNP‐LA, upon 808 nm NIR light irradiation, exhibit obviously higher toxicity at the cellular and animal levels compared with chemotherapy or photothermal therapy alone, indicating the PEG‐OJNP‐LA could be utilized as a multifunctional nanoplatform for in vitro and in vivo actively‐targeted and chemo‐photothermal cancer therapy.
Temporal Control of Gelation and Polymerization Fronts Driven by an Autocatalytic Enzyme Reaction
Authors: Jee Elizabeth , Bánsági Tamás , Taylor Annette F. , Pojman John A.
Published: January 2016

Chemical systems that remain kinetically dormant until activated have numerous applications in materials science. Herein we present a method for the control of gelation that exploits an inbuilt switch: the increase in pH after an induction period in the urease‐catalyzed hydrolysis of urea was used to trigger the base‐catalyzed Michael addition of a water‐soluble trithiol to a polyethylene glycol diacrylate. The time to gelation (minutes to hours) was either preset through the initial concentrations or the reaction was initiated locally by a base, thus resulting in polymerization fronts that converted the mixture from a liquid into a gel (ca. 0.1 mm min−1). The rate of hydrolytic degradation of the hydrogel depended on the initial concentrations, thus resulting in a gel lifetime of hours to months. In this way, temporal programming of gelation was possible under mild conditions by using the output of an autocatalytic enzyme reaction to drive both the polymerization and subsequent degradation of a hydrogel.
Spin‐Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible‐Light Photosensitization of Azidoformates
Authors: Scholz Spencer O. , Farney Elliot P. , Kim Sangyun , Bates Desiree M. , Yoon Tehshik P.
Published: January 2016

Azidoformates are interesting potential nitrene precursors, but their direct photochemical activation can result in competitive formation of aziridination and allylic amination products. Herein, we show that visible‐light‐activated transition‐metal complexes can be triplet sensitizers that selectively produce aziridines through the spin‐selective photogeneration of triplet nitrenes from azidoformates. This approach enables the aziridination of a wide range of alkenes and the formal oxyamination of enol ethers using the alkene as the limiting reagent. Preparative‐scale aziridinations can be easily achieved under continuous‐flow conditions.
Gelled Complex Fluids: Combining Unique Structures with Mechanical Stability
Authors: Stubenrauch Cosima , Gießelmann Frank
Published: January 2016

Gelled complex fluids are soft materials in which the microstructure of the complex fluid is combined with the mechanical stability of a gel. To obtain a gelled complex fluid one either adds a gelator to a complex fluid or replaces the solvent in a gel by a complex fluid. The most prominent example of a “natural” gelled complex fluid is the cell. There are various strategies by which one can form a gelled complex fluid; one such strategy is orthogonal self‐assembly, that is, the independent but simultaneous formation of two coexisting self‐assembled structures within one system. The aim of this Review is to describe the structure and potential applications of various man‐made gelled complex fluids and to clarify whether or not the respective system is formed by orthogonal self‐assembly.
Bent Carbon Surface Moieties as Active Sites on Carbon Catalysts for Phosgene Synthesis
Authors: Gupta Navneet K. , Pashigreva Anastasia , Pidko Evgeny A. , Hensen Emiel J. M. , Mleczko Leslaw , Roggan Stefan , Ember Erika E. , Lercher Johannes A.
Published: January 2016

Active sites in carbon‐catalyzed phosgene synthesis from gaseous CO and Cl2 have been identified using C60 fullerene as a model catalyst. The carbon atoms distorted from sp2 coordination in non‐planar carbon units are concluded to generate active Cl2. Experiments and density functional theory calculations indicate the formation of a surface‐bound [C60⋅⋅⋅Cl2] chlorine species with radical character as key intermediate during phosgene formation. It reacts rapidly with physisorbed CO in a two‐step Eley–Rideal‐type mechanism.
Graphene Oxide Catalyzed C−H Bond Activation: The Importance of Oxygen Functional Groups for Biaryl Construction
Authors: Gao Yongjun , Tang Pei , Zhou Hu , Zhang Wei , Yang Hanjun , Yan Ning , Hu Gang , Mei Donghai , Wang Jianguo , Ma Ding
Published: January 2016

A heterogeneous, inexpensive, and environmentally friendly graphene oxide catalytic system for the C−H bond arylation of benzene enables the formation of biaryl compounds in the presence of aryl iodides. The oxygen functional groups in these graphene oxide sheets and the addition of KOtBu are essential for the observed catalytic activity. Reactions with various model compounds and DFT calculations confirmed that these negatively charged oxygen atoms promote the overall transformation by stabilizing and activating K+ ions, which in turns facilitates the activation of the C−I bond. However, the graphene π system also greatly facilitates the overall reaction as the aromatic coupling partners are easily adsorbed.
Oxidative Coupling of Aryl Boron Reagents with sp3‐Carbon Nucleophiles: The Enolate Chan–Evans–Lam Reaction
Authors: Moon Patrick J. , Halperin Heather M. , Lundgren Rylan J.
Published: January 2016

Reported is a versatile new oxidative method for the arylation of activated methylene species. Under mild reaction conditions (RT to 40 °C), Cu(OTf)2 mediates the selective coupling of functionalized aryl boron species with a variety of stabilized sp3‐nucleophiles. Tertiary malonates and amido esters can be employed as substrates to generate quaternary centers. Complementing either traditional cross‐coupling or SNAr protocols, the transformation is chemoselective in the presence of halogen electrophiles, including aryl bromides and iodides. Substrates bearing amide, sulfonyl, and phosphonyl groups, which are not amenable to coupling under mild Hurtley‐type conditions, are suitable reaction partners.
A new magnetic nanoparticle‐supported Schiff base complex of manganese: an efficient and recyclable catalyst for selective oxidation of alcohols
Authors: Zhou Qiangfei , Wan Zijuan , Yuan Xiaofeng , Luo Jun
Published: January 2016

A new magnetic nanoparticle‐supported Schiff base complex of manganese was prepared via the copper‐catalyzed ‘click’ reaction of an aminosalicylidene manganese complex bearing terminal alkynyl with azide‐functionalized shell–core magnetic nanoparticles. The as‐prepared catalyst was applied in the oxidation of alcohols to corresponding aldehydes or ketones with high yield and selectivity when the reaction was carried out in dimethylsulfoxide at 110°C for 4 h using tert‐butyl hydroperoxide as oxidant. Moreover, the catalyst can be easily separated from the reaction mixture using an external magnet and reused five times with no significant loss of catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.
In‐situ monitoring of Saccharomyces cerevisiaeITV01 bioethanol process using near‐infrared spectroscopy NIRS and chemometrics
Authors: Corro‐Herrera Víctor Abel , Gómez‐Rodríguez Javier , Hayward‐Jones Patricia Margaret , Barradas‐Dermitz Dulce María , Aguilar‐Uscanga María Guadalupe , Gschaedler‐Mathis Anne Christine
Published: January 2016

The application feasibility of in‐situ or in‐line monitoring of S. cerevisiae ITV01 alcoholic fermentation process, employing Near‐Infrared Spectroscopy (NIRS) and Chemometrics, was investigated. During the process in a bioreactor, in the complex analytical matrix, biomass, glucose, ethanol and glycerol determinations were performed by a transflection fiber optic probe immersed in the culture broth and connected to a Near‐Infrared (NIR) process analyzer. The NIR spectra recorded between 800 and 2,200 nm were pretreated using Savitzky‐Golay smoothing and second derivative in order to perform a partial least squares regression (PLSR) and generate the calibration models. These calibration models were tested by external validation and then used to predict concentrations in batch alcoholic fermentations. The standard errors of calibration (SEC) for biomass, ethanol, glucose and glycerol were 0.212, 0.287, 0.532, and 0.296 g/L and standard errors of prediction (SEP) were 0.323, 0.369, 0.794, and 0.507 g/L, respectively. Calibration and validation criteria were defined and evaluated in order to generate robust and reliable models for an alcoholic fermentation process matrix. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:510–517, 2016
Probing Supramolecular Interactions between a Crown Ether Appended Zinc Phthalocyanine and an Ammonium Group Appended to a C60 Derivative
Authors: Lederer Marcus , Hahn Uwe , Strub Jean‐Marc , Cianférani Sarah , Van Dorsselaer Alain , Nierengarten Jean‐François , Torres Tomas , Guldi Dirk M.
Published: January 2016

Self‐assembly driven by crown ether complexation of zinc phthalocyanines equipped with one 18‐crown‐6 moiety and fullerenes bearing an ammonium head group afforded a novel donor–acceptor hybrid. In reference experiments, fullerenes containing a Boc‐protected amine functionality have been probed. The circumvention of zinc phthalocyanine aggregation is important for the self‐assembly, which required the addition of pyridine. From absorption and fluorescence titration assays, which provided sound and unambiguous evidence for mutual interactions between the electron donor and the electron acceptor within the hybrids, association constants in the order of 8.0×105 m−1 have been derived. The aforementioned is based on 1:1 stoichiometries, which have been independently confirmed by Job's plot measurements. In the excited state, which has been examined by transient absorption experiments, intermolecular charge separation evolves from the photoexcited zinc phthalocyanine to the fullerene subunit and leads to short‐lived charge‐separated states. Interestingly, photoexcitation of zinc phthalocyanine dimers/aggregates can also be followed by an intermolecular charge separation between vicinal phthalocyanines. These multicomponent supramolecular ensembles have also been shown by in‐depth electrospray ionization mass spectrometry (ESI‐MS) studies, giving rise to the formation and detection of a variety of non‐covalently linked species.
S‐Trifluoromethylation of Thiols by Hypervalent Iodine Reagents: A Joint Experimental and Computational Study
Authors: Sala Oliver , Santschi Nico , Jungen Stefan , Lüthi Hans Peter , Iannuzzi Marcella , Hauser Nicole , Togni Antonio
Published: January 2016

The radical trifluoromethylation of thiophenol in condensed phase applying reagent 1 (3,3‐dimethyl‐1‐(trifluoromethyl)‐1λ3,2‐benziodoxol) has been examined by both theoretical and experimental methodologies. On the basis of ab initio molecular dynamics and metadynamics we show that radical reaction mechanisms favourably compete with polar ones involving the S‐centred nucleophile thiophenol, their free energies of activation, ΔF≠, lying between 9 and 15 kcal mol−1. We further show that the origin of the proton activating the reagent is important. Hammett plot analysis reveals intramolecular protonation of 1, thus generating negative charge on the sulfur atom in the rate‐determining step. The formation of a CF3 radical can be thermally induced by internal dissociative electron transfer, its activation energy, ΔF≠, amounting to as little as 10.8 and 2.8 kcal mol−1 for reagent 1 and its protonated form 2, respectively. The reduction of the iodine atom by thiophenol occurs either subsequently or in a concerted fashion.
ChemInform Abstract: Two Types of 2D Layered Iodoargentates Based on Trimeric [Ag3I7] Secondary Building Units and Hexameric [Ag6I12] Ternary Building Units: Syntheses, Crystal Structures, and Efficient Visible Light Responding Photocatalytic Properties.
Authors: Yue Cheng‐Yang , et al.
Published: January 2016

Compounds (IV), (VI), and (VII) are characterized by single crystal XRD, UV/VIS diffuse reflectance spectroscopy, and DFT calculations.
ChemInform Abstract: Gold‐Catalyzed Cyclization of Propargylic Diynes: Ethers vs Acetates — Related Products but Different Pathways.
Authors: Schaedlich Johannes , Lauterbach Tobias , Rudolph Matthias , Rominger Frank , Hashmi A. Stephen K.
Published: January 2016

A protocol for the gold‐catalyzed cycloisomerization of propargyl ethers bearing a second triple bond is presented.
ChemInform Abstract: Base‐Promoted/Gold‐Catalyzed Intramolecular Highly Selective and Controllable Detosylative Cyclization.
Authors: Zhu Chenghao , Qiu Lin , Xu Guangyang , Li Jian , Sun Jiangtao
Published: January 2016

The base‐promoted, metal‐free intramolecular detosylative cyclization of bi‐N‐tosylhydrazones affords a wide range of N‐containing heterocycles and can be practically utilized in preparing pyridazines, diazepines, and related heterocycles.
ChemInform Abstract: Transfer Hydrogenation Promoted by N‐Heterocyclic Carbene and Water.
Authors: Kato Terumasa , Matsuoka Shin‐ichi , Suzuki Masato
Published: January 2016

The successful application of the title reaction to a broad range of electron‐deficient alkenes is described, including maleates and fumarates, Michael‐acceptors, imines, carbodiimides and azodicarboxylates.
ChemInform Abstract: Ligand‐Free Copper‐Mediated N‐Arylation of Spirocyclic Lactams.
Authors: Yang Wei , Coutinho Ana Luisa , Abdel‐Hafez Atef A. , Jiang Chao , Xue Fengtian
Published: January 2016

The coupling of aryl iodides with lactams (I) tolerates various functional groups in both partners to give N‐arylated products in good yields.
ChemInform Abstract: Transition‐Metal‐Free Cross‐Coupling of Aryl and N‐Heteroaryl Cyanides with Benzylic Zinc Reagents.
Authors: Quinio Pauline , Roman Daniela Sustac , Leon Thierry , William Sharankini , Karaghiosoff Konstantin , Knochel Paul
Published: January 2016

A coupling reaction of benzylic zinc chlorides and 4‐pyridinenitriles under microwave irradiation gives 4‐benzylpyridines efficiently.
ChemInform Abstract: Asymmetric Nitrocyclopropanation of α‐Substituted α,β‐Enals Catalyzed by Diphenylprolinol Silyl Ether for the Construction of All‐Carbon Quaternary Stereogenic Centers.
Authors: Hayashi Yujiro , Yamazaki Tatsuya , Nakanishi Yuki , Ono Tsuyoshi , Taniguchi Tohru , Monde Kenji , Uchimaru Tadafumi
Published: January 2016

The first step in the title reaction proceeds with good to excellent enantioselectivity and the cis‐isomer is generally the major one.
ChemInform Abstract: Silver‐Mediated Oxidative Trifluoromethylation of Phenols: Direct Synthesis of Aryl Trifluoromethyl Ethers.
Authors: Liu Jian‐Bo , Chen Chao , Chu Lingling , Chen Zeng‐Hao , Xu Xiu‐Hua , Qing Feng‐Ling
Published: January 2016

Ag(I)‐mediated conversion of structurally diverse phenols to their CF3‐ethers is achieved using CF3‐SiMe3 as commercially available CF3‐nucleophile.
ChemInform Abstract: Copper‐Catalyzed Ligand‐Free Amidation of Benzylic Hydrocarbons and Inactive Aliphatic Alkanes.
Authors: Zeng Hui‐Ting , Huang Jing‐Mei
Published: January 2016

A wide range of N‐alkylated amides, sulfonamides, and imides are synthesized in the presence of catalytic amounts of CuCl and KOtBu.
ChemInform Abstract: Transition‐Metal‐Free α‐Arylation of Enolizable Aryl Ketones and Mechanistic Evidence for a Radical Process.
Authors: Pichette Drapeau Martin , Fabre Indira , Grimaud Laurence , Ciofini Ilaria , Ollevier Thierry , Taillefer Marc
Published: January 2016

Various aryl ketones are efficiently transformed via the reaction with aryliodides, bromides, and chlorides.
ChemInform Abstract: Amine‐Catalyzed Highly Regioselective and Stereoselective C(sp2)—C(sp2) Cross‐Coupling of Naphthols with trans‐α,β‐Unsaturated Aldehydes.
Authors: Hu Yang , Ma Yueyue , Sun Rengwei , Yu Xinhong , Xie Hexin , Wang Wei
Published: January 2016

The reaction of 1‐naphthol (I) and substituted analogues (VI) with various unsaturated aldehydes under conditions A) in the presence of piperidine affords exclusively C‐4 substituted, highly functionalized derivatives as (E) isomers (E:Z < 95:5).
ChemInform Abstract: Gold(I)‐Catalyzed Tandem Transformation with Diynes: Rapid Access to Linear Cyclopentenone‐Fused Polycyclic Molecules.
Authors: Yu Congjun , Chen Bin , Zhou Tian , Tian Qingshan , Zhang Guozhu
Published: January 2016

Conditions A) allow a rapid access to a broad spectrum of title ring systems where a wide variety of functionalities is tolerated.
ChemInform Abstract: Facile Ligand‐Free Pd‐Catalyzed Tandem C—C/C—N Coupling Reaction: A Novel Access to Highly Diverse Tetrazole Tag Isoindoline Derivatives.
Authors: Sharma Moni , Khan Irfan , Khan Shahnawaz , Mahar Rohit , Shukla Sanjeev K. , Kant Ruchir , Chauhan Prem M.S.
Published: January 2016

For the first time, an efficient method for the synthesis of tetrazole‐isoindoline via palladium‐catalyzed cyclization with isocyanide insertion is demonstrated.
ChemInform Abstract: Cu(I)—NHC‐Catalyzed [2 + 3]‐Annulation of Tetramic Acids with 2H‐Azirines: Stereoselective Synthesis of Functionalized Hexahydropyrrolo[3,4‐b]pyrroles.
Authors: Rostovskii Nikolai V. , Sakharov Pavel A. , Novikov Mikhail S. , Khlebnikov Alexander F. , Starova Galina L.
Published: January 2016

Various 3‐aryl and 3‐methoxycarbonyl substituted tetramic acid derivatives are efficiently transformed with 2‐ 3‐aryl or alkyl substituted 2H‐azirines.
ChemInform Abstract: Molecular‐Oxygen‐Promoted Cu‐Catalyzed Oxidative Direct Amidation of Nonactivated Carboxylic Acids with Azoles.
Authors: Ding Wen , Mai Shaoyu , Song Qiuling
Published: January 2016

The title reaction probably proceeds via a copper peroxycarboxylate intermediate.
ChemInform Abstract: Synthesis of 3,4,5‐Trisubstituted Isoxazoles from Morita—Baylis—Hillman Acetates by an NaNO2/I2‐Mediated Domino Reaction.
Authors: Dighe Shashikant U. , Mukhopadhyay Sushobhan , Kolle Shivalinga , Kanojiya Sanjeev , Batra Sanjay
Published: January 2016

Addition of NaNO2 to the starting acetates under conditions A) leads to formation of the required highly functionalized isoxazole derivatives (mechanism).
ChemInform Abstract: Regio‐ and Enantioselective Aza‐Diels—Alder Reactions of 3‐Vinylindoles: A Concise Synthesis of the Antimalarial Spiroindolone NITD609.
Authors: Zheng Haifeng , Liu Xiaohua , Xu Chaoran , Xia Yong , Lin Lili , Feng Xiaoming
Published: January 2016

The title reaction with isatin‐derived ketimines opens the access to various functionalized polycyclic N‐heterocycles which include a spirooxindolone unit.
ChemInform Abstract: Expedient One‐Pot Synthesis of Indolo[3,2‐c]isoquinolines via a Base‐Promoted N‐Alkylation/Tandem Cyclization.
Authors: Nguyen Huy H. , Fettinger James C. , Haddadin Makhluf J. , Kurth Mark J.
Published: January 2016

Transition metal‐free and operationally simple one‐pot protocol for the synthesis of the title compounds is developed starting from readily available ethyl (2‐cyanophenyl)carbamates and 2‐cyanobenzyl bromides.
ChemInform Abstract: Access to Imidazo[1,2‐a]pyridines via Annulation of α‐Keto Vinyl Azides and 2‐Aminopyridines.
Authors: Adiyala Praveen Reddy , Mani Geeta Sai , Nanubolu Jagadeesh Babu , Shekar Kunta Chandra , Maurya Ram Awatar
Published: January 2016

An unprecedented annulation of vinyl azides and 2‐aminopyridines is achieved under thermal conditions to give imidazo[1,2‐a]pyridines in excellent yields.
ChemInform Abstract: Multicomponent Synthesis of Uracil Analogues Promoted by Pd‐Catalyzed Carbonylation of α‐Chloroketones in the Presence of Isocyanates and Amines.
Authors: Perrone Serena , Capua Martina , Salomone Antonio , Troisi Luigino
Published: January 2016

A short, one‐pot synthesis of uracil derivatives with high structural variability is established.
ChemInform Abstract: An Efficient Green Protocol for the Preparation of Acetoacetamides and Application of the Methodology to a One‐Pot Synthesis of Biginelli Dihydropyrimidines. Expansion of Dihydropyrimidine Topological Chemical Space.
Authors: Gama Fernando H. S. , de Souza Rodrigo O. M. A. , Garden Simon J.
Published: January 2016

The title acetoacetamides are obtained from various amine derivatives and dioxin‐4‐one by conventional and microwave‐assisted heating.
ChemInform Abstract: Catalytic Synthesis of N‐Unprotected Piperazines, Morpholines, and Thiomorpholines from Aldehydes and SnAP Reagents.
Authors: Luescher Michael U. , Bode Jeffrey W.
Published: January 2016

Ring closure of various aliphatic and (hetero)aromatic aldehydes with stannyl amine substrates under slightly differentiated conditions renders possible the access to a broad spectrum of the title compounds.
ChemInform Abstract: Ag(I)‐Catalyzed Three‐Component Reaction of 2‐Alkynylbenzaldehydes, Amines, and Diazo Compounds.
Authors: Xiao Tiebo , Peng Pai , Xie Yang , Wang Zhao‐yang , Zhou Lei
Published: January 2016

A one‐pot three‐component cyclization of diazo compounds as nucleophiles with primary aromatic amines and alkynylbenzaldehydes gives 3‐benzazepines via a cascade imine—yne cyclization/nucleophilic addition/1,2‐aryl migrations.
ChemInform Abstract: FeCl2‐Catalyzed Hydroboration of Aryl Alkenes with Bis(pinacolato)diboron.
Authors: Liu Yang , Zhou Yuhan , Wang Huan , Qu Jingping
Published: January 2016

A novel protocol is presented for a ligand‐free ferrous chloride‐catalyzed hydroboration of non‐activated aryl alkenes.
ChemInform Abstract: Synthesis of Fluoroalkoxy Substituted Arylboronic Esters by Iridium‐Catalyzed Aromatic C—H Borylation.
Authors: Batool Farhat , Parveen Shehla , Emwas Abdul‐Hamid , Sioud Salim , Gao Xin , Munawar Munawar A. , Chotana Ghayoor A.
Published: January 2016

The regioselectivities available through this convenient and efficient borylation reaction are complementary to those obtained by the electrophilic aromatic substitution reactions of fluoroalkoxyarenes.
ChemInform Abstract: A Robust and Simple Protocol for the Synthesis of Arylfluorophosphonates.
Authors: Leypold Mario , Wallace Paal W. , Kljajic Marko , Schittmayer Matthias , Pletz Jakob , Illaszewicz‐Trattner Carina , Guebitz Georg M. , Birner‐Gruenberger Ruth , Breinbauer Rolf
Published: January 2016

A sequence is developed for the conversion of arylphosphonic acids into arylfluorophosphonates through selective monoesterification and subsequent fluorination.
ChemInform Abstract: A New Dimeric Naphtho‐γ‐pyrone from an Endophytic Fungus Aspergillus niger AKRN Associated with the Roots of Entandrophragma congoense Collected in Cameroon
Authors: Happi Gervais M. , Kouam Simeon Fogue , Talontsi Ferdinand M. , Nkenfou Celine N. , Longo Frida , Zuehlke Sebastian , Douanla‐Meli Clovis , Spiteller Michael
Published: January 2016

isolation and structure elucidation of 2‐hydroxydihydronigerone (I)
ChemInform Abstract: First Total Synthesis of Antimalarial (+)‐Cryptorigidifoliol A.
Authors: Raju Atla , Yugendar Reddy A. , Sabitha Gowravaram
Published: January 2016

The first total synthesis of antimalarial (+)‐cryptorigidifoliol A is accomplished by two different approaches in 6 and 5 steps with overall yields of 45% and 33%.
ChemInform Abstract: Isolation and Structure of Vanitaracin A, a Novel Antihepatitis B Virus Compound from Talaromyces sp.
Authors: Matsunaga Hiroki , Kamisuki Shinji , Kaneko Manabu , Yamaguchi Yasuhiro , Takeuchi Toshifumi , Watashi Koichi , Sugawara Fumio
Published: January 2016

Two tricyclic polyketides, vanitaracin A (Ia) and B (Ib), and compounds (II), (III), and (IV) are isolated from a culture broth of title fungus and tested for their anti‐HBV activity.
ChemInform Abstract: Benzofuran: An Emerging Scaffold for Antimicrobial Agents
Authors: Hiremathad Asha , Patil Mahadeo R. , Chethana K. R. , Chand Karam , Santos M. Amelia , Rangappa S. Keri
Published: January 2016

Review: [125 refs.
ChemInform Abstract: Transition‐Metal‐Catalyzed Cleavage of C‐N Single Bonds
Authors: Ouyang Kunbing , Hao Wei , Zhang Wen‐Xiong , Xi Zhenfeng
Published: January 2016

Review: 319 refs.
ChemInform Abstract: Principles and Applications of Enantioselective Hydroformylation of Terminal Disubstituted Alkenes
Authors: Deng Yuchao , Wang Hui , Sun Yuhan , Wang Xiao
Published: January 2016

Review: 79 refs.
ChemInform Abstract: Heterogeneously Catalyzed Alcohol Oxidation for the Fine Chemical Industry
Authors: Ciriminna Rosaria , Pandarus Valerica , Beland Francois , Xu Yi‐Jun , Pagliaro Mario
Published: January 2016

Review: 56 refs.
ChemInform Abstract: Contemporary Asymmetric Phase Transfer Catalysis: Large‐Scale Industrial Applications
Authors: Tan Jiajing , Yasuda Nobuyoshi
Published: January 2016

Review: [70 refs.
ChemInform Abstract: High‐Capacity Electrode Materials for Electrochemical Energy Storage: Role of Nanoscale Effects
Authors: Nanda Jagjit , Martha Surendra K. , Kalyanaraman Ramki
Published: January 2016

Review: 46 refs.
ChemInform Abstract: Intrinsic Reaction Coordinate: Calculation, Bifurcation, and Automated Search
Authors: Maeda Satoshi , Harabuchi Yu , Ono Yuriko , Taketsugu Tetsuya , Morokuma Keiji
Published: January 2016

Review: 173 refs.
Tribal diversity, human resources management practices, and firm performance
Authors: Zoogah David B.
Published: January 2016

This study explores the relationship between tribal diversity, human resources management practices, and firm performance in Africa. Using multiple data sources and multilevel techniques, I examine tribal diversity as a driver of human resource management‐diversity policy (HRM‐DP) and an interactive factor influencing firm performance. Tribal identity is also tested as a determinant of tribal diversity. The results show that HRM‐DP mediates the relationship between tribal diversity and firm performance. Tribal identity also relates negatively to tribal diversity, HRM‐DP, and firm performance. Lastly, tribal diversity interacts with tribal identity in relating to firm performance. Theoretical and practical implications are discussed to enhance tribal diversity management in Africa. Copyright © 2016 ASAC. Published by John Wiley & Sons, Ltd.
Gas‐to‐liquids processes: Preface
Authors: Patience Gregory S. , Boffito Daria C.
Published: January 2016

XtL refers to a collection of technologies that convert natural gas, biomass, coal, and petroleum coke (X) to liquid fuels, waxes, and chemicals (L). GtL (Gas‐to‐Liquids) is a class of XtL that refers specifically to natural gas, which includes producing syngas; removing sulphur compounds, metals, and other contaminants; and reacting the syngas to either Fischer‐Tropsh fuels (FT), gasoline, alcohols, aldehydes, DME, or olefins. Converting natural gas continues to inspire academic research and industry as a means of tackling global warming, adding value to waste streams, and improving the environment. The Web of Science indexed 6400 papers regarding Fischer‐Tropsch in the last 25 years (600 papers in 2014, which is a three‐fold increase versus the late 1990s) and Derwent indexed 3500 patents.
Molecular classification of thyroid lesions by combined testing for miRNA gene expression and somatic gene alterations
Authors: Wylie Dennis , Beaudenon‐Huibregtse Sylvie , Haynes Brian C. , Giordano Thomas J. , Labourier Emmanuel
Published: January 2016

Multiple molecular markers contribute to the pathogenesis of thyroid cancer and can provide valuable information to improve disease diagnosis and patient management. We performed a comprehensive evaluation of miRNA gene expression in diverse thyroid lesions (n = 534) and developed predictive models for the classification of thyroid nodules, alone or in combination with genotyping. Expression profiling by reverse transcription‐quantitative polymerase chain reaction in surgical specimens (n = 257) identified specific miRNAs differentially expressed in 17 histopathological categories. Eight supervised machine learning algorithms were trained to discriminate benign from malignant lesions and evaluated for accuracy and robustness. The selected models showed invariant area under the receiver operating characteristic curve (AUC) in cross‐validation (0.89), optimal AUC (0.94) in an independent set of preoperative thyroid nodule aspirates (n = 235), and classified 92% of benign lesions as low risk/negative and 92% of malignant lesions as high risk/positive. Surgical and preoperative specimens were further tested for the presence of 17 validated oncogenic gene alterations in the BRAF, RAS, RET or PAX8 genes. The miRNA‐based classifiers complemented and significantly improved the diagnostic performance of the 17‐mutation panel (p < 0.001 for McNemar's tests). In a subset of resected tissues (n = 54) and in an independent set of thyroid nodules with indeterminate cytology (n = 42), the optimized ThyraMIR Thyroid miRNA Classifier increased diagnostic sensitivity by 30–39% and correctly classified 100% of benign nodules negative by the 17‐mutation panel. In contrast, testing with broad targeted next‐generation sequencing panels decreased diagnostic specificity by detecting additional mutations of unknown clinical significance in 19–39% of benign lesions. Our results demonstrate that, independent of mutational status, miRNA expression profiles are strongly associated with altered molecular pathways underlying thyroid tumorigenesis. Combined testing for miRNA gene expression and well‐established somatic gene alterations is a novel diagnostic strategy that can improve the preoperative diagnosis and surgical management of patients with indeterminate thyroid nodules.
A sliding window‐based dynamic load balancing for heterogeneous Hadoop clusters
Authors: Liu Yang , Jing Weizhe , Liu Youbo , Lv Lin , Qi Man , Xiang Yang
Published: January 2016

At present MapReduce computing model‐based Hadoop framework has gradually become the most famous distributed computing framework because of its remarkable features such as scalability, fault tolerance, data security, and powerful IO ability. However, Hadoop framework only supports limited load balancing policies, which may result in performance deterioration in heterogeneous clusters. Additionally Hadoop does not have advanced dynamic load balancing mechanism in enabling its optimal performance in dynamic environment. This paper presents a sliding window‐based dynamic load balancing algorithm, which specially aims at balancing the load among the heterogeneous nodes during the Hadoop job processing. The presented algorithm is evaluated in both simulated and physical environments. The experimental results show that the performances in terms of efficiency of Hadoop cluster can be significantly improved. Copyright © 2016 John Wiley & Sons, Ltd.
Photocatalytic Water Oxidation over Metal Oxide Nanosheets Having a Three‐Layer Perovskite Structure
Authors: Oshima Takayoshi , Eguchi Miharu , Maeda Kazuhiko
Published: January 2016

Metal oxide nanosheets having a three‐layer perovskite structure were studied as photocatalysts for water oxidation in the presence of IO3− as a reversible electron acceptor. This work examined the effects of the lateral dimensions and composition of the nanosheets as well as metal oxide co‐catalysts deposited on the restacked nanosheets. Depositing metal oxides capable of promoting reduction reactions on the nanosheets were found to promote the water oxidation activity. In contrast, the lateral dimensions and the degree of crystallinity of the nanosheets had little effect on the activity. Experimental results demonstrated that the reduction of IO3− is the rate‐limiting step in this reaction and that nanosheets with less distorted structures are advantageous with regard to increasing both light absorption and the mobility of photoexcited charge carriers.