bluuebunny/crossref_metadata_2025 huggingface dataset:
Rationalization of the Color Properties of Fluorescein in the Solid State: A Combined Computational and Experimental Study
Authors: Arhangelskis Mihails , Eddleston Mark D. , Reid David G. , Day Graeme M. , Bučar Dejan‐Krešimir , Morris Andrew J. , Jones William
Published: June 2016

Fluorescein is known to exist in three tautomeric forms defined as quinoid, zwitterionic, and lactoid. In the solid state, the quinoid and zwitterionic forms give rise to red and yellow materials, respectively. The lactoid form has not been crystallized pure, although its cocrystal and solvate forms exhibit colors ranging from yellow to green. An explanation for the observed colors of the crystals is found using a combination of UV/Vis spectroscopy and plane‐wave DFT calculations. The role of cocrystal coformers in modifying crystal color is also established. Several new crystal structures are determined using a combination of X‐ray and electron diffraction, solid‐state NMR spectroscopy, and crystal structure prediction (CSP). The protocol presented herein may be used to predict color properties of materials prior to their synthesis.
Magnesium Lewis Acid Assisted Oxidative Bromoetherification Involving Bromine Transfer from Alkyl Bromides with Aldehydes by Umpolung of Bromide
Authors: Moriyama Katsuhiko , Nishinohara Chihiro , Togo Hideo
Published: June 2016

An oxidative bromoetherification involving a bromine transfer from alkyl bromides upon reacting them with aldehydes in a Grignard reaction with a concurrent oxidation of bromide was developed to provide substituted tetrahydrofurans in high yields. This reaction, which proceeds through two types of bromine transfer, was promoted by the addition of a Brønsted acid. Mechanistic studies suggested that a magnesium Lewis acid activates hypobromate, which is generated in situ from the reaction of bromide and Oxone to improve the electrophilicity of the bromonium ion (Br+) for the oxidative bromoetherification of alkenyl alcohols. Furthermore, the magnesium Lewis acid catalyzed oxidative bromoetherification of an alkenyl alcohol proceeded to provide a cyclization product in 92 % yield.
Self‐Immolative Linkers as Caps for the Design of Gated Silica Mesoporous Supports
Authors: Juárez L. Alberto , Añón Elena , Giménez Cristina , Sancenón Félix , Martínez‐Máñez Ramón , Costero Ana M. , Gaviña Pablo , Parra Margarita , Bernardos Andrea
Published: June 2016

A new hybrid material based on sulforhodamine B dye‐loaded silica mesoporous nanoparticles capped with a self‐immolative gate has been synthesized and characterized. The gated material's controlled release behavior is monitored under different pH conditions. Under acidic and neutral conditions, a low level of dye release is detected. However, at slightly basic pH, significant dye release occurs owing to deprotonation of the phenol moiety in the capping molecule, which results in its disassembly.
Synthesis of 2‐Alkynoates by Palladium(II)‐Catalyzed Oxidative Carbonylation of Terminal Alkynes and Alcohols
Authors: Cao Qun , Hughes N. Louise , Muldoon Mark J.
Published: June 2016

A homogeneous PdII catalyst, utilizing a simple and inexpensive amine ligand (TMEDA), allows 2‐alkynoates to be prepared in high yields by an oxidative carbonylation of terminal alkynes and alcohols. The catalyst system overcomes many of the limitations of previous palladium carbonylation catalysts. It has an increased substrate scope, avoids large excesses of alcohol substrate and uses a desirable solvent. The catalyst employs oxygen as the terminal oxidant and can be operated under safer gas mixtures.
Label‐Free Detection of Glycan–Protein Interactions for Array Development by Surface‐Enhanced Raman Spectroscopy (SERS)
Authors: Li Xiuru , Martin Sharon J. H. , Chinoy Zoeisha S. , Liu Lin , Rittgers Brandon , Dluhy Richard A. , Boons Geert‐Jan
Published: June 2016

A glyco‐array platform has been developed, in which glycans are attached to plasmonic nanoparticles through strain‐promoted azide‐alkyne cycloaddition. Glycan–protein binding events can then be detected in a label‐free manner employing surface‐enhanced Raman spectroscopy (SERS). As proof of concept, we have analyzed the binding of Gal1, Gal3, and influenza hemagglutinins (HAs) to various glycans and demonstrated that binding partners can be identified with high confidence. The attraction of SERS for optical sensing is that it can provide unique spectral signatures for glycan–protein complexes, confirm identity through statistical validation, and minimizes false positive results common to indirect methods. Furthermore, SERS is very sensitive and has multiplexing capabilities thereby allowing the simultaneous detection of multiple analytes.
ChemInform Abstract: A Molten Salt Lithium—Oxygen Battery.
Authors: Giordani Vincent , Tozier Dylan , Tan Hongjin , Burke Colin M. , Gallant Betar M. , Uddin Jasim , Greer Julia R. , McCloskey Bryan D. , Chase Gregory V. , Addison Dan
Published: June 2016

A Li/O2 battery using a Li anode, molten LiNO3—KNO3 or LiNO3—KNO2—CsNO3 eutectic electrolytes, and a porous carbon O2 cathode at 120—150 °C exhibits high energy efficiency of about 95% and improved rate capability.
ChemInform Abstract: A One‐Dimensional Polyoxomolybdate Polymer as a Catalyst for the Epoxidation of Olefins.
Authors: Najafi M. , Abbasi A. , Masteri‐Farahani M. , Shahbaazi H. , Ahmadniai Motlagh M. , Janczak J.
Published: June 2016

The one‐dimensional coordination polymer {(NH4)4Mo8O26}n is hydrothermally synthesized from an aqueous mixture of (NH4)6Mo7O24, ZnCl2, HCl, and terephthalic acid (autoclave, 140 °C, 4 d).
ChemInform Abstract: Layered Perovskite Oxychloride Bi4NbO8Cl: A Stable Visible Light Responsive Photocatalyst for Water Splitting.
Authors: Fujito Hironori , Kunioku Hironobu , Kato Daichi , Suzuki Hajime , Higashi Masanobu , Kageyama Hiroshi , Abe Ryu
Published: June 2016

The title material is prepared by solid state reaction of a stoichiometric mixture of Bi2O3, BiOCl, and Nb2O5 (evacuated silica tube, 1173 K, 20 h) and characterized by powder XRD and UV/VIS diffuse reflectance spectroscopy.
ChemInform Abstract: Face‐Shared Octahedral Dimer In2O7S2 in the Non‐Centrosymmetric Barium Indiumsilicate Oxysulfide Ba2In2Si3O10S.
Authors: Guo Wei‐Huan , Jiang Xiao‐Ming , Liu Bin‐Wen , Wu Jia‐Wei , Li Shu‐Fang , Zeng Hui‐Yi , Guo Guo‐Cong , Huang Jin‐Shun
Published: June 2016

Single crystals of the new title compound are obtained from an alkali polychalcogenide flux consisting of K2S, S, In, SiO2, and BaCl2 in a molar ratio of 2:2:4:1:4 (evacuated quartz tubes, 1.
ChemInform Abstract: Efficient Access to Multifunctional Trifluoromethyl Alcohols Through Base‐Free Catalytic Asymmetric C—Bond Formation with Terminal Ynamides.
Authors: Cook Andrea M. , Wolf Christian
Published: June 2016

The first catalytic enantioselective addition of terminal ynamides to trifluoromethyl ketones is developed.
ChemInform Abstract: Copper(I) Chloride Promoted C(sp2)—N Cross‐Coupling of 1,2‐Di(pyrimidin‐2‐yl) Disulfides with Amines: An Efficient Approach to Obtain C2‐Amino Functionalized Pyrimidines.
Authors: Wei Kai‐Jie , Quan Zheng‐jun , Zhang Zhang , Da Yu‐xia , Wang Xi‐cun
Published: June 2016

A protocol for chemoselective transformation of disulfides into aryl and alkyl amines is developed.
ChemInform Abstract: Engaging Alkenyl Halides with Alkylsilicates via Photoredox Dual Catalysis.
Authors: Patel Niki R. , Kelly Christopher B. , Jouffroy Matthieu , Molander Gary A.
Published: June 2016

Ammonium organobis(catecholato)silicates, serving as radical precursors, and alkenyl halides are cross‐coupled via dual photoredox/Ni catalysis.
ChemInform Abstract: Selective N‐Acetylation of Aromatic Amines Using Acetonitrile as Acylating Agent.
Authors: Saikia Ujwal Pratim , Hussain Farhaz L. , Suri Mrinaly , Pahari Pallab
Published: June 2016

The new method for the N‐acetylation of aromatic amines uses acetonitrile as an acylating agent and in situ generated trimethylsilyl iodide as the catalyst under microwave irradiation.
ChemInform Abstract: Enhancement of N‐Heterocyclic Carbenes on Rhodium Catalyzed Olefination of Triazoles.
Authors: Zhao Shixian , Wu Feifei , Ma Yuyu , Chen Wanzhi , Liu Miaochang , Wu Huayue
Published: June 2016

Using carbene transfer reactions, four new rhodium complexes of N‐heterocyclic carbenes, e.g. RHC, are prepared.
ChemInform Abstract: Metal‐Free Intermolecular Hydrophenoxylation of Aryl Alkynes.
Authors: Patel Monika , Saunthwal Rakesh K. , Dhaked Devendra K. , Bharatam Prasad V. , Verma Akhilesh K.
Published: June 2016

Terminal as well as internal alkynes react with phenols and alkanols in an anti‐Markovnikov fashion giving β‐arylvinyl ethers in good yields with excellent Z selectivity.
ChemInform Abstract: A Route to α‐Fluoroalkyl Sulfides from α‐Fluorodiaroylmethanes.
Authors: Lin Ya‐mei , Yi Wen‐bin , Shen Wan‐zhao , Lu Guo‐ping
Published: June 2016

α,α‐Difluorodiarylmethanes are successfully used as nucleophilic difluoromethylation reagents to generate α‐thioaryl‐α,α‐difluoroacetophenones or difluoromethylthiolated arenes from disulfides under transition‐metal free conditions.
ChemInform Abstract: 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: June 2016

The oxygen sites in the graphene oxide catalyst and the addition of potassium tert‐butoxide are found to be essential for this novel direct C—H arylation method.
ChemInform Abstract: Gold‐Catalyzed Intramolecular Cyclizations of Cyclopropenes with Propargylic Esters.
Authors: Zhu Peng‐Long , Tang Xiang‐Ying , Shi Min
Published: June 2016

A gold‐catalyzed intramolecular cycloisomerization of cyclopropenes, N‐ or O‐tethered, affords 5‐azaspiro[2.5]oct‐7‐enes and bicyclo[4.1.0]heptanes depending on the substitution pattern.
ChemInform Abstract: Catalytic Oxidative Coupling of Primary Amines under Air: A Flexible Route to Benzimidazole Derivatives.
Authors: Nguyen Khac Minh Huy , Largeron Martine
Published: June 2016

In a bioinspired approach, the cooperative action of cupric bromide as electron‐transfer mediator and a topaquinone‐like co‐catalyst is studied.
ChemInform Abstract: 4‐Aryl‐NH‐1,2,3‐triazoles via Multicomponent Reaction of Aldehydes, Nitroalkanes, and Sodium Azide.
Authors: Wu Luyong , Wang Xianghui , Chen Yuxue , Huang Qinglan , Lin Qiang , Wu Mingshu
Published: June 2016

This novel approach to the title compounds works well with aromatic aldehydes only: cinnamaldehyde and octanal do not react while phenylglyoxal hydrate (VI) gives 4‐phenyl‐1,2,3‐triazole (IIIa) in low yield only.
ChemInform Abstract: Application of Novel Multi‐Cationic Ionic Liquids in Microwave Assisted 2‐Amino‐4H‐chromene Synthesis.
Authors: Kumbhar Arjun , Jadhav Sanjay , Shejwal Rajendra , Rashinkar Gajanan , Salunkhe Rajshri
Published: June 2016

The newly prepared ionic liquid (CIL) is used for the microwave‐assisted multicomponent cyclocondensation of naphthols with aromatic aldehydes and malononitrile to give aminochromenes.
ChemInform Abstract: Heteropolyacid‐Catalyzed One‐Pot Synthesis of 2‐Pyridone Derivatives.
Authors: Samzadeh‐Kermani Alireza
Published: June 2016

The catalyst can be recovered by simple filtration and reused, with a decrease in yield observed in the 4th run.
ChemInform Abstract: 1,1′‐Carbonyldiimidazole (CDI) Mediated Coupling and Cyclization to Generate [1,2,4]Triazolo[4,3‐a]pyridines.
Authors: Baucom Kyle D. , Jones Sian C. , Roberts Scott W.
Published: June 2016

A CDI mediated coupling of 2‐pyridylhydrazines and carboxylic acids followed by cyclization reaction to generate [1,2,4]triazolo[4,3‐a]pyridines is reported.
ChemInform Abstract: One‐Pot, Highly Efficient, Asymmetric Synthesis of Ring‐Fused Piperidine Derivatives Bearing N,O‐ or N,N‐Acetal Moieties.
Authors: Li Ji‐Yao , Li Zhi‐Long , Zhao Wei‐Wei , Liu Yan‐Kai , Tong Zhi‐Ping , Tan Rui
Published: June 2016

This stereoselective method relies on an organo‐catalyzed asymmetric Diels—Alder reaction/iminium ion‐induced cyclization sequence.
ChemInform Abstract: The First Catalytic Asymmetric Thioacetalization by Chiral Phosphoric Acid Catalysis.
Authors: Yu Jin‐Sheng , Wu Wen‐Biao , Zhou Feng
Published: June 2016

The first catalytic asymmetric thioacetalization of salicylaldehyde and dithiol is reported.
ChemInform Abstract: The Base‐Promoted Synthesis of Multisubstituted Benzo[b][1,4]oxazepines.
Authors: Shen Jinhai , Xue Lulu , Lin Xing , Cheng Guolin , Cui Xiuling
Published: June 2016

Reaction conditions are optimized for the base promoted cyclization of N‐(2‐haloaryl)enaminones which offer a simple access to substituted benzo[b][1,4]oxazepines in moderate to good yields.
ChemInform Abstract: A Versatile One‐Pot Strategy for the Synthesis of [1,4]Thiazepino[5,4‐a]isoquinolines Containing Intramolecular Hydrogen Bonds.
Authors: Alizadeh Abdolali , Bayat Fahimeh , Zhu Zhe
Published: June 2016

The title compounds are constructed via a sequential 4‐component domino reaction from phenacylbromides, isoquinoline, aryl isothiocyanates and DMAD in good yields.
ChemInform Abstract: Highly Efficient Solvent Free Synthesis of α‐Aminophosphonates Catalyzed by Recyclable Nano‐Magnetic Sulfated Zirconia (Fe3O4@ZrO2/SO42‐).
Authors: Ghafuri Hossein , Rashidizadeh Afsaneh , Esmaili Zand Hamid Reza
Published: June 2016

An environmentally benign method for preparation of the aminophosphonates via Kabachnik—Fields reaction using sulfated zirconia supported on magnetic nanoparticles is developed.
ChemInform Abstract: Lanostane‐Type Triterpenes from the Fungal Endophyte Scleroderma UFSMSc1 (Persoon) Fries.
Authors: Morandini Liziane M.B. , Neto Alexandre T. , Pedroso Marcelo , Antoniolli Zaida I. , Burrow Robert A. , Bortoluzzi Adailton J. , Mostardeiro Marco A. , da Silva Ubiratan F. , Dalcol Ionara I. , Morel Ademir F.
Published: June 2016

Two lanostane triterpenoids, sclerodol A (Ia) and B (Ib), are isolated from the culture of Eucalyptus grandis derived from the endophyte Scleroderma UFSMSc1 (Persoon) Fries.
ChemInform Abstract: A New Concept for Electroless Nickel Plating: Aluminum as Reducing Agent.
Authors: Zhang Xingkai , Zhang Junyan
Published: June 2016

Nickel coatings on Cu substrates are obtained using plating baths containing only NiSO4, ammonia, and an Al foil connected to the Cu substrate that serves as the electron source for Ni deposition (20 °C, 30 min).
ChemInform Abstract: Interactions Between Lasers and Two‐Dimensional Transition Metal Dichalcogenides
Authors: Lu Junpeng , Liu Hongwei , Tok Eng Soon , Sow Chorng‐Haur
Published: June 2016

Review: focus on the use of laser‐based technologies as effective tools for the characterization, modification, and manipulation of transition metal dichalcogenides; 113 refs.
ChemInform Abstract: Three‐Dimensional Electrocatalysts for Sustainable Water Splitting Reactions
Authors: Zhao Hui , Zhu Yun‐Pei , Yuan Zhong‐Yong
Published: June 2016

Review: 83 refs.
ChemInform Abstract: The Applications of Nano‐Hetero‐Junction in Optical and Thermal Catalysis
Authors: Liao Fenglin , Lo Benedict T. W. , Tsang Edman
Published: June 2016

Review: 88 refs.
ChemInform Abstract: Marine‐Derived Myxobacteria of the Suborder Nannocystineae: An Underexplored Source of Structurally Intriguing and Biologically Active Metabolites
Authors: Davila‐Cespedes Antonio , Hufendiek Peter , Cruesemann Max , Schaeberle Till F. , Koenig Gabriele M.
Published: June 2016

Review: [85 refs.
ChemInform Abstract: Recent Developments in Multicomponent Synthesis of Structurally Diversified Tetrahydropyridines
Authors: Khan Md. Musawwer , Khan Sarfaraz , Iqbal Saigal , Iqbal Safia
Published: June 2016

Review: [61 refs.
ChemInform Abstract: Stable Silanetriols‐Building Blocks for Rings and Cages
Authors: Pietschnig Rudolf
Published: June 2016

Review: 19 refs.
ChemInform Abstract: C—C Bond Formation on Activation of Alkynes and Alkenes with (C5R5)Ru Catalysts
Authors: Derien Sylvie
Published: June 2016

Review: 136 refs.
ChemInform Abstract: A Short Review on the Magnetic Effects Occurring at Organic Ferromagnetic Interfaces Formed Between Benzene‐Like Molecules and Graphene with Ferromagnetic Surfaces
Authors: Atodiresei Nicolae , Caciuc Vasile , Lazic Predrag
Published: June 2016

Review: 42 refs.
ChemInform Abstract: Review on Fungal Enzyme Inhibitors — Potential Drug Targets to Manage Human Fungal Infections
Authors: Ramakrishnan Jayapradha , Rathore Sudarshan Singh , Raman Thiagarajan
Published: June 2016

Review: 148 refs.
Visualisierung der DNA‐Doppelhelixstruktur mit einfachen Mitteln
Authors: Quadbeck‐Seeger Hans‐Jürgen
Published: June 2016

Die Doppelhelix der DNA ist zur Ikone der modernen Biologie und der Medizin geworden. Inzwischen begegnen uns ständig Abbildungen dieser molekularen Struktur. Dabei handelt es sich in der Regel um die B‐Form der DNA, die in der Natur vorherrscht und um die es auch in diesem Artikel geht. Es ist allerdings erstaunlich, wie oft deren Darstellungen falsch sind oder Unzutreffendes andeuten.
On the effect of temperature on precipitation and aggregation of asphaltenes in light live oils
Authors: Mohammadi Saber , Rashidi Fariborz , Mousavi‐Dehghani Sayed Ali , Ghazanfari Mohammad‐Hossein
Published: June 2016

Asphaltene precipitation and deposition is a serious issue in all facets of petroleum production and processing. Despite the numerous experimental efforts concerning asphaltenes, the effect of temperature on asphaltene precipitation and aggregation in live oils remains an elusive and controversial subject in the available literature. In this work, a series of high pressure‐high temperature depressurization experiments were designed to assess the effect of temperature on asphaltene precipitation and aggregation in light live oils. Asphaltene related experiments were performed using a high pressure microscope and high pressure‐high temperature filtration setup on a light live oil with a low asphaltene content and a high potential of asphaltene formation. The results of the experiments were interpreted in terms of asphaltene onset pressure, size distribution and average diameter of the aggregates, fractal dimension of the asphaltene aggregates, and the amount of precipitated asphaltene. It was found that the depressurization process at higher temperatures resulted in higher asphaltene onset pressure or earlier formation of asphaltenes. Visualization experiments showed that asphaltene aggregates in light live oil are pressure‐temperature fractal structures. The depressurization process at lower temperatures led to the formation of highly porous and loose aggregate structures with relatively low fractal dimensions. As the temperature of the depressurization process decreases, the mechanism of asphaltene aggregation changes gradually from reaction‐limited aggregation to diffusion‐limited aggregation. This research reveals that temperature has crucial effects on the asphaltene aggregation process in light live oils at elevated pressures, which is of great importance for asphaltene handling and separation.
Synthesis of Highly Stable Porous Metal‐Iminodiacetic Acid Gels from A Novel IDA Compound
Authors: Chen Wenjing , Jiang Yanhong , Ding Xuesong , Yan Chaoguo , Han Baohang
Published: June 2016

In this work, a novel and simple flexible aromatic multi‐carboxylate compound N,N′‐(4,4′‐biphenylyl) iminodiacetic acid (BP‐IDA) was synthesized, with which two new stable metal‐IDA gels (denoted as MIG1 and MIG2) with three‐dimensional network structures have been prepared successfully by employing Cr3+ and Al3+ as the metal ions, respectively. The rheological performance was investigated by means of dynamic rheology measurement. The morphology and microstructure were characterized by scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction technique. Nitrogen sorption isotherm measurement suggests that the MIG1 aerogel has considerable porosity with the Brunauer‐Emmett‐Teller specific surface area up to 760 m2·g−1. Owing to easy preparation, good stability, and three‐dimensional network structure, the as‐prepared metal‐organic gels will possess potential applications in separation, catalysis, and drug delivery.
Recent Progress in the Application of Polyoxometalates for Dye‐sensitized/Organic Solar Cells
Authors: Ye Tengling , Wang Junhai , Dong Guohua , Jiang Yanxia , Feng Chen , Yang Yulin
Published: June 2016

At present, high efficiency and low fabrication cost are still the main goal that people pursuit for next‐generation solar cells such as dye‐sensitized solar cells (DSSCs) and organic solar cells (OPVs). Polyoxometalates (POMs), as an environmentally friendly material, are a type of stable, low cost and soluble oxide clusters with desirable features, including highly tunable structural properties, peculiar optoelectronic properties and excellent redox properties. Thus, during the recent years, POMs have been increasingly recognized as important building blocks for DSSCs and OPVs. In this review, the development of various molecular and hybrid materials derived from POMs is discussed with regard to the function in solar cells.
Permeabilization activated reduction in fluorescence: A novel method to measure kinetics of protein interactions with intracellular structures
Authors: Singh Pali P. , Hawthorne Jenci L. , Davis Christie A. , Quintero Omar A.
Published: June 2016

Understanding kinetic information is fundamental in understanding biological function. Advanced imaging technologies have fostered the development of kinetic analyses in cells. We have developed Permeabilization Activated Reduction in Fluorescence (PARF) analysis for determination of apparent t1/2 and immobile fraction, describing the dissociation of a protein of interest from intracellular structures. To create conditions where dissociation events are observable, cells expressing a fluorescently‐tagged protein are permeabilized with digitonin, diluting the unbound protein into the extracellular media. As the media volume is much larger than the cytosolic volume, the concentration of the unbound pool decreases drastically, shifting the system out of equilibrium, favoring dissociation events. Loss of bound protein is observed as loss of fluorescence from intracellular structures and can be fit to an exponential decay. We compared PARF dissociation kinetics with previously published equilibrium kinetics as determined by FRAP. PARF dissociation rates agreed with the equilibrium‐based FRAP analysis predictions of the magnitude of those rates. When used to investigate binding kinetics of a panel of cytoskeletal proteins, PARF analysis revealed that filament stabilization resulted in slower fluorescence loss. Additionally, commonly used “general” F‐actin labels display differences in kinetic properties, suggesting that not all fluorescently‐tagged actin labels interact with the actin network in the same way. We also observed differential dissociation kinetics for GFP‐VASP depending on which cellular structure was being labeled. These results demonstrate that PARF analysis of non‐equilibrium systems reveals kinetic information without the infrastructure investment required for other quantitative approaches such as FRAP, photoactivation, or in vitro reconstitution assays. © 2016 Wiley Periodicals, Inc.
Discovery of New Potential Anti‐Infective Compounds Based on Carbonic Anhydrase Inhibitors by Rational Target‐Focused Repurposing Approaches
Authors: Annunziato Giannamaria , Angeli Andrea , D'Alba Francesca , Bruno Agostino , Pieroni Marco , Vullo Daniela , De Luca Viviana , Capasso Clemente , Supuran Claudiu T. , Costantino Gabriele
Published: June 2016

In academia, compound recycling represents an alternative drug discovery strategy to identify new pharmaceutical targets from a library of chemical compounds available in house. Herein we report the application of a rational target‐based drug‐repurposing approach to find diverse applications for our in‐house collection of compounds. The carbonic anhydrase (CA, EC 4.2.1.1) metalloenzyme superfamily was identified as a potential target of our compounds. The combination of a thoroughly validated docking screening protocol, together with in vitro assays against various CA families and isoforms, allowed us to identify two unprecedented chemotypes as CA inhibitors. The identified compounds have the capacity to preferentially bind pathogenic (bacterial/protozoan) CAs over human isoforms and represent excellent hits for further optimization in hit‐to‐lead campaigns.
Longitudinal analysis of patient‐reported outcomes and cosmesis in a randomized trial of conventionally fractionated versus hypofractionated whole‐breast irradiation
Authors: Swanick Cameron W. , Lei Xiudong , Shaitelman Simona F. , Schlembach Pamela J. , Bloom Elizabeth S. , Fingeret Michelle C. , Strom Eric A. , Tereffe Welela , Woodward Wendy A. , Stauder Michael C. , Dvorak Tomas , Thompson Alastair M. , Buchholz Thomas A. , Smith Benjamin D.
Published: June 2016

BACKGROUND

The authors compared longitudinal patient‐reported outcomes and physician‐rated cosmesis with conventionally fractionated whole‐breast irradiation (CF‐WBI) versus hypofractionated whole‐breast irradiation (HF‐WBI) within the context of a randomized trial.

METHODS

From 2011 to 2014, a total of 287 women with American Joint Committee on Cancer stage 0 to stage II breast cancer were randomized to receive CF‐WBI (at a dose of 50 grays in 25 fractions plus a tumor bed boost) or HF‐WBI (at a dose of 42.56 grays in 16 fractions plus a tumor bed boost) after breast‐conserving surgery. Patient‐reported outcomes were assessed using the Breast Cancer Treatment Outcome Scale (BCTOS), the Functional Assessment of Cancer Therapy‐Breast, and the Body Image Scale and were recorded at baseline and 0.5, 1, 2, and 3 years after radiotherapy. Physician‐rated cosmesis was assessed at the same time points. Outcomes by treatment arm were compared at each time point using a 2‐sided Student t test. Multivariable mixed effects growth curve models assessed the effects of treatment arm and time on longitudinal outcomes.

RESULTS

Of the 287 patients enrolled, 149 were randomized to CF‐WBI and 138 were randomized to HF‐WBI. At 2 years, the Functional Assessment of Cancer Therapy‐Breast Trial Outcome Index score was found to be modestly better in the HF‐WBI arm (mean 79.6 vs 75.9 for CF‐WBI; P = .02). In multivariable mixed effects models, treatment arm was not found to be associated with longitudinal outcomes after adjusting for time and baseline outcome measures (P≥.14). The linear effect of time was significant for BCTOS measures of functional status (P = .001, improved with time) and breast pain (P = .002, improved with time).

CONCLUSIONS

In this randomized trial, longitudinal outcomes did not appear to differ by treatment arm. Patient‐reported functional and pain outcomes improved over time. These findings are relevant when counseling patients regarding decisions concerning radiotherapy. Cancer 2016. © 2016 American Cancer Society. Cancer 2016;122:2886–2894. © 2016 American Cancer Society
Fluorescence Quenching of Benzaldehyde in Water by Hydrogen Atom Abstraction
Authors: Fletcher Katharyn , Bunz Uwe H. F. , Dreuw Andreas
Published: June 2016

We computed the mechanism of fluorescence quenching of benzaldehyde in water through relaxed potential energy surface scans. Time‐dependent density functional theory calculations along the protonation coordinate from water to benzaldehyde reveal that photoexcitation to the bright ππ* (S3) state is immediately followed by ultrafast decay to the nπ* (S1) state. Evolving along this state, benzaldehyde (BA) abstracts a hydrogen atom, resulting in a BAH. and OH. radical pair. Benzaldehyde does not act as photobase in water, but abstracts a hydrogen atom from a nearby solvent molecule. The system finally decays back to the ground state by non‐radiative decay and an electron transfers back to the OH. radical. Proton transfer from BAH+ to OH− restores the initial situation, BA in water.
Potential Energy Surfaces and Charge Transfer of PAH‐Sodium‐PAH Complexes
Authors: Hjertenæs Eirik , Andersson Stefan , Koch Henrik
Published: June 2016

To further understanding of the role of sodium in carbon cathode degradation in Hall–Héroult cells, potential‐energy surfaces and charge‐transfer curves are presented for finite‐size complexes of sodium intercalated between various polycyclic aromatic hydrocarbons. Calculations for lithium and potassium are included to highlight the disparate intercalation behaviour of the alkali metals in graphite intercalation compounds. Static energy barriers from DFT are used to compute macroscopic diffusion coefficients according to transition‐state theory. Comparing the calculated diffusion coefficient to experimental values from the literature sheds light on the role of lattice diffusion of sodium–graphite intercalation compounds in sodium intrusion in graphitic carbon cathodes.
Engineering Chemically Exfoliated Large‐Area Two‐Dimensional MoS2 Nanolayers with Porphyrins for Improved Light Harvesting
Authors: Zhang Hanyu , Choi Jungwook , Ramani Arjun , Voiry Damien , Natoli Sean N. , Chhowalla Manish , McMillin David R. , Choi Jong Hyun
Published: June 2016

Molybdenum disulfide (MoS2) is a promising candidate for electronic and optoelectronic applications. However, its application in light harvesting has been limited in part due to crystal defects, often related to small crystallite sizes, which diminish charge separation and transfer. Here we demonstrate a surface‐engineering strategy for 2D MoS2 to improve its photoelectrochemical properties. Chemically exfoliated large‐area MoS2 thin films were interfaced with eight molecules from three porphyrin families: zinc(II)‐, gallium(III)‐, iron(III)‐centered, and metal‐free protoporphyrin IX (ZnPP, GaPP, FePP, H2PP); metal‐free and zinc(II) tetra‐(N‐methyl‐4‐pyridyl)porphyrin (H2T4, ZnT4); and metal‐free and zinc(II) tetraphenylporphyrin (H2TPP, ZnTPP). We found that the photocurrents from MoS2 films under visible‐light illumination are strongly dependent on the interfacial molecules and that the photocurrent enhancement is closely correlated with the highest occupied molecular orbital (HOMO) levels of the porphyrins, which suppress the recombination of electron–hole pairs in the photoexcited MoS2 films. A maximum tenfold increase was observed for MoS2 functionalized with ZnPP compared with pristine MoS2 films, whereas ZnT4‐functionalized MoS2 demonstrated small increases in photocurrent. The application of bias voltage on MoS2 films can further promote photocurrent enhancements and control current directions. Our results suggest a facile route to render 2D MoS2 films useful for potential high‐performance light‐harvesting applications.
A new paradigm for predicting risk of Torsades de Pointes during drug development: Commentary on: “Improved prediction of drug‐induced Torsades de Pointes through simulations of dynamics and machine learning algorithms”
Authors: McCauley MD , Darbar D
Published: June 2016

Drug‐induced long QT syndrome (diLQTS) is a clinical entity in which administration of a drug produces marked prolongation of the QT interval on the ECG. DiLQTS places a patient at risk of developing Torsades de Pointes (TdP), a malignant polymorphic ventricular tachycardia associated with arrhythmic sudden cardiac death (SCD). In addition to diLQTS, other clinical risk factors for TdP include female gender, bradycardia, electrolyte disturbances, recent conversion to normal (sinus) rhythm, and congenital LQTS.
Poly(ethylenimine)‐Functionalized Monolithic Alumina Honeycomb Adsorbents for CO2 Capture from Air
Authors: Sakwa‐Novak Miles A. , Yoo Chun‐Jae , Tan Shuai , Rashidi Fereshteh , Jones Christopher W.
Published: June 2016

The development of practical and effective gas–solid contactors is an important area in the development of CO2 capture technologies. Target CO2 capture applications, such as postcombustion carbon capture and sequestration (CCS) from power plant flue gases or CO2 extraction directly from ambient air (DAC), require high flow rates of gas to be processed at low cost. Extruded monolithic honeycomb structures, such as those employed in the catalytic converters of automobiles, have excellent potential as structured contactors for CO2 adsorption applications because of the low pressure drop imposed on fluid moving through the straight channels of such structures. Here, we report the impregnation of poly(ethylenimine) (PEI), an effective aminopolymer reported commonly for CO2 separation, into extruded monolithic alumina to form structured CO2 sorbents. These structured sorbents are first prepared on a small scale, characterized thoroughly, and compared with powder sorbents with a similar composition. Despite consistent differences observed in the filling of mesopores with PEI between the monolithic and powder sorbents, their performance in CO2 adsorption is similar across a range of PEI contents. A larger monolithic cylinder (1 inch diameter, 4 inch length) is evaluated under conditions closer to those that might be used in large‐scale applications and shows a similar performance to the smaller monoliths and powders tested initially. This larger structure is evaluated over five cycles of CO2 adsorption and steam desorption and demonstrates a volumetric capacity of 350 mol
 
and an equilibration time of 350 min under a 0.4 m s−1 linear flow velocity through the monolith channels using 400 ppm CO2 in N2 as the adsorption gas at 30 °C. This volumetric capacity surpasses that of a similar technology considered previously, which suggested that CO2 could be removed from air at an operating cost as low as $100 per ton.
“Strong beats skinny every time”: Disordered eating and compulsive exercise in women who post fitspiration on Instagram
Authors: Holland Grace , Tiggemann Marika
Published: June 2016

Objective

Fitspiration is a recent Internet trend designed to motivate people to eat healthily and to exercise. The aim of the study was to investigate disordered eating and exercise in women who post fitspiration on Instagram.

Method

Participants were 101 women who post fitspiration images on Instagram and a comparison group of 102 women who post travel images. Both groups completed measures of disordered eating and compulsive exercise.

Results

Women who post fitspiration images scored significantly higher on drive for thinness, bulimia, drive for muscularity, and compulsive exercise. Almost a fifth (17.5%) of these women were at risk for diagnosis of a clinical eating disorder, compared to 4.3% of the travel group. Compulsive exercise was related to disordered eating in both groups, but the relationship was significantly stronger for women who post fitspiration images.

Discussion

For some women, posting fitspiration images on Instagram may signify maladaptive eating and exercise behaviors. © 2016 Wiley Periodicals, Inc. (Int J Eat Disord 2017; 50:76–79)
Cognitive‐behavioral treatment of adult rumination behavior in the setting of disordered eating: A single case experimental design
Authors: Thomas Jennifer J. , Murray Helen B.
Published: June 2016

The integration of feeding and eating disorders into a single DSM‐5 chapter introduces an opportunity to explore common mechanisms and transdiagnostic treatment approaches. In contrast to a robust literature on the evidence‐based treatment of eating disorders, very few data guide the treatment of rumination disorder (RD). In a single case experimental design, we describe the treatment of a 27‐year‐old woman who presented to an eating‐disorder clinic with a 15‐year history of untreated rumination and intermittent binge eating. According to time series analysis, she reduced rumination frequency at trend‐level during the initial baseline phase (self‐monitoring only), and exhibited significant reductions during the active intervention phase (self‐monitoring + cognitive‐behavioral techniques including diaphragmatic breathing and behavioral experimentation). She maintained these gains at 23 weeks post‐intervention. Although more rigorous systematic investigation is needed, these data suggest that selected cognitive and behavioral techniques already familiar to eating‐disorder clinicians may have heuristic value for RD treatment. © 2016 Wiley Periodicals, Inc. (Int J Eat Disord 2016; 49:967–972)
Facebook usage among those who have received treatment for an eating disorder in a group setting
Authors: Saffran Kristina , Fitzsimmons‐Craft Ellen E. , Kass Andrea E. , Wilfley Denise E. , Taylor Craig Barr , Trockel Mickey
Published: June 2016

Objective

This study explored Facebook use among individuals with a history of receiving treatment for an eating disorder (ED) in a group setting (e.g., inpatient, residential, outpatient group), focusing primarily on comparisons individuals make about their bodies, eating, or exercise to those of their peers from treatment on Facebook and the relation between these comparisons and ED pathology.

Method

Individuals (N = 415; mean age 28.15 years ± 8.41; 98.1% female) who self‐reported receipt of ED treatment in a group setting were recruited via e‐mail and social media to complete an online survey.

Results

Participants reported having an average of 10–19 Facebook friends from treatment and spending up to 30 min per day interacting on Facebook with individuals from treatment or ED‐related organizations. More comparison to treatment peers on Facebook was associated with greater ED psychopathology and ED‐related impairment. Conversely, positive interaction with treatment peers on Facebook was associated with lower ED psychopathology and ED‐related impairment. Individuals who had been in treatment longer, more times, and more recently had more Facebook friends from treatment and ED‐related organizations as well as spent more time in ED groups' pages on Facebook. Few participants (19.5%) reported that a therapist asked about the impact of Facebook on pathology.

Discussion

Interactions on Facebook could affect patients' recovery and potential for relapse. It may be helpful for treatment providers to discuss Facebook use and its potential benefits and drawbacks with patients preparing for discharge from group treatment. © 2016 Wiley Periodicals, Inc. (Int J Eat Disord 2016; 49:764–777)
Increased temporal discounting in bulimia nervosa
Authors: Kekic Maria , Bartholdy Savani , Cheng Jiumu , McClelland Jessica , Boysen Elena , Musiat Peter , O'Daly Owen G. , Campbell Iain C. , Schmidt Ulrike
Published: June 2016

Objective

There is evidence that people with eating disorders display altered intertemporal choice behavior (the degree of preference for immediate rewards over delayed rewards). Compared to healthy controls (HC), individuals with anorexia nervosa and binge‐eating disorder show decreased and increased rates of temporal discounting (TD; the devaluation of delayed rewards), respectively. This is the first study to investigate TD in people with bulimia nervosa (BN).

Method

Thirty‐nine individuals with BN (2 men) and 53 HC (9 men) completed a hypothetical monetary TD task. Over 80 binary choices, participants chose whether they would prefer to receive a smaller amount of money available immediately or a larger amount available in 3 months. Self‐reported ability to delay gratification (the behavioral opposite of TD) was also measured.

Results

Individuals with BN showed greater TD (i.e., a preference for smaller‐sooner rewards) and a decreased self‐reported capacity to delay gratification relative to HC. Experimental groups did not differ in age, gender ratio, or BMI.

Discussion

Increased rates of TD may contribute to some of the core symptoms of BN that appear to involve making choices between immediate and delayed rewards (i.e., binge‐eating and compensatory behaviors). Altered intertemporal choice behavior could therefore be a relevant target for intervention in this patient group. © 2016 Wiley Periodicals, Inc. (Int J Eat Disord 2016; 49:1077–1081)
Four‐, Five‐, and Six‐Coordinate Silicon(IV) Complexes: Reactivity of the Donor‐Stabilized Silylenes [iPrNC(Ph)NiPr]2Si and [iPrNC(NiPr2)NiPr]2Si Towards Me3SiN3 and PhSCH2N3
Authors: Mück Felix M. , Förster Bettina , Baus Johannes A. , Nutz Marco , Burschka Christian , Bertermann Rüdiger , Tacke Reinhold
Published: June 2016

Bis(amidinato)silylene 1 and the analogous bis(guanidinato)silylene 2 reacted with Me3SiN3 to form compounds 3 [a five‐coordinate silicon(IV) complex with an Si=N double bond] and 4 [a four‐coordinate silicon(IV) complex with an Si=N double bond], respectively. For compound 3, a dynamic equilibrium between a five‐ and four‐coordinate silicon(IV) species in solution was observed (at –95 °C, these species are stable on the NMR spectroscopic timescale), whereas 4 is four‐coordinate in solution. Treatment of 1 with PhSCH2N3 afforded compound 5 (isolated as 5a·5b·0.5n‐C6H14), which is a cocrystallizate of the diastereomers 5a and 5b with half an n‐hexane molecule in the asymmetric unit. The diastereomers 5a and 5b [six‐coordinate silicon(IV) complexes with an unsubstituted methyleneamido ligand and an SiN5S skeleton] differ only in their interchanged positions of their thiophenolato and methyleneamido ligands. In solution, a dynamic equilibrium between 5a and 5b was observed.
Multifaceted Bicubane Co4 Clusters: Magnetism, Photocatalytic Oxygen Evolution, and Electrical Conductivity
Authors: Xie Wan‐Feng , Guo Ling‐Yu , Xu Jia‐Heng , Jagodič Marko , Jagličić Zvonko , Wang Wen‐Guang , Zhuang Gui‐Lin , Wang Zhi , Tung Chen‐Ho , Sun Di
Published: June 2016

The use of 1‐(hydroxymethyl)‐3,5‐dimethylpyrazole (HL), a functionalized pyrazole ligand, to assemble with CoX2 (X = Cl or Br) in the presence of triethylamine under low‐temperature solvothermal conditions gave rise to two tetranuclear cobalt(II) clusters, [Co4L6X2] [X = Cl (1), Br (2)]. Both CoII4 clusters are isostructural and protected by four µ2‐N1:O2 and two µ3‐N1:O3L– as well as terminal X anions to form a face‐shared open bicubane structural motif. Magnetic susceptibility measurements indicated that there is an intramolecular antiferromagnetic interaction between four CoII atoms in 1 and 2. Although the core motif of 1 and 2 is not classic Co4O4 monocubane, both are active catalysts for water oxidation, and their relative O2‐evolution rates are dependent on the halogen terminal ligands, which is also supported by spin‐polarized density functional theory (DFT) calculations. Both clusters exhibit semiconductor behavior with σ values on the 10–9 S cm–1 scale at room temperature; however, mechanical iodine doping results in up to an astonishing 105‐fold maximum enhancement of solid‐state conductivity relative to the undoped samples. This work therefore presents a new core type of cobalt cluster that possesses photocatalytic oxygen‐evolution capabilities, provides new insight into the catalysis‐related mechanism based on the relative oxygen‐evolution efficiency, and applies the iodine‐doping strategy to boost the conductivity of cluster compounds.
Perspective of vibrational spectroscopy analytical methods in on‐field/official control of olives and virgin olive oil
Authors: Nenadis Nikolaos , Tsimidou Maria Z.
Published: June 2016

Vibrational spectroscopic techniques, infrared (near, mid, far) and Raman that are based on the continuous vibrational motion of the atoms in the corresponding bonds of the compounds correlate in a unique way the physical properties of materials in the gaseous, solid, or liquid state with the molecular structure. Olive industry and olive oil official control may benefit from the introduction of these powerful techniques to address quality and authenticity issues. This review focuses on evidence obtained from comparative studies among different vibrational techniques for the same set/s of samples or from the same instrumentation. It also assists the forum of discussion on what is needed for their standardization in order to find their place in the official control of the end product. The need for validation guidelines regarding the management of the instrument as well as the construction of the calibration model is highlighted. The latter depends heavily on the reference method employed. An extended list of references covering the characteristics of the techniques, advancements in instrumentation, general applications to oils and fats, and those useful for on‐field and official control of olive and olive oil is also given.

Practical application: Vibrational spectroscopic techniques coupled to chemometrics can modernize olive and olive oil analysis from the field to the official control at the borders and in the market. As it occurs already for many decades in the field of other high added value commodities, i.e., milk, meat, wine, the value of the multiple type of information acquired with little sample manipulation should be recognized by all interested parties in the olive sector (stakeholders, authorities, researchers).

Qualitative and quantitative information from field to the table (quality, adulteration, authentication).
Label‐free Electrochemical Impedance Detection of Rotavirus Based on Immobilized Antibodies on Gold Sononanoparticles
Authors: Attar Aisha , Mandli Jihane , Ennaji My Mustapha , Amine Aziz
Published: June 2016

Currently, rotaviruses (RVs) are the leading cause of severe childhood gastroenteritis worldwide. This study proposes a sensitive and simple label‐free assay for determining rotaviruses using, for the first time, electrochemical impedance spectroscopy (EIS). The immunosensor is fabricated by self‐assembled monolayers (SAMs) of cysteamine on gold sononanoparticles (AuSNPs) modified glassy carbon electrode. The electron transfer resistance (Ret) of the electrode interface was adopted as a parameter for the detection of rotavirus. Using the proposed immunosensor, a good linear relationship (r2=0.993) between impedance change and logarithmic value of rotaviruses in a wide range of 4.6 to 4.6×104 PFU mL−1 was found, with a low limit of detection (LOD) 2.3 PFU mL−1 and a total analysis time of 55 min. Working parameters of the immunosensor, such as pH, antibodies concentration and immune‐reaction time, have been investigated and optimized. No obvious interferences from non‐target viruses such as hepatitis A virus (HAV) and enterovirus were found. In addition, the electrochemical impedance immunosensor has exhibited good sensitivity, selectivity and stability.
Role of Conductive Nanoparticles in the Direct Unmediated Bioelectrocatalysis of Immobilized Sulfite Oxidase
Authors: Zeng Ting , Frasca Stefano , Rumschöttel Jens , Koetz Joachim , Leimkühler Silke , Wollenberger Ulla
Published: June 2016

We report efficient bioelectrocatalytic sulfite oxidation by human sulfite oxidase (hSO) immobilized on a gold nanoparticle (AuNP) modified gold electrode. The AuNP were synthesized in aqueous phase by using branched polyethyleneimine (PEI) as reducing as well as stabilizing agent. Gold electrodes were modified by a self assembled monolayer of dithio‐bis(N‐hydroxysuccinimidyl propionate) (DTSP) onto which the NP and hSO were immobilized. Cyclic voltammetry of the hSO modified electrode in the absence of substrate revealed a quasi‐reversible direct electrochemical reaction of the heme domain of hSO with fast electron transfer rate. The electron transfer rate constant of ks=32 s−1 and the formal potential E0′=−0.155 V vs. Ag/AgCl/1 M KCl were estimated. Comparative studies with nanoparticles of BaSO4 indicate the importance of the NP conductivity for charge transfer and enhancement of direct electron transfer communication. Sulfite addition resulted in a largely enhanced oxidation current at low overpotential. Use of longer thiols for assembly of the AuNP resulted in a decrease of electron transfer rate and increase of overpotential for sulfite bioelectrocatalysis. The electrode modified with DTSP and AuNP exhibited a very high steady state catalytic current density of 1 µA/cm2. The assembly can be applied for the amperometric biosensing of sulfite at a potential of 0 mV vs. Ag/AgCl/1 M KCl.