bluuebunny/crossref_metadata_2025_split huggingface dataset:
Chiroptical Spectra of Tetrakis (+)‐3‐Heptafluorobutylrylcamphorate Ln(III) Complexes with an Encapsulated Alkali Metal Ion: Solution Structures as Revealed by Chiroptical Spectra
Authors: Shirotani Dai , Yamanari Kazuaki , Kuroda Reiko , Harada Takunori , Lunkley Jamie L. , Muller Gilles , Sato Hisako , Kaizaki Sumio 
Published: September 2012

ABSTRACTThe preparation of tetrakis((+)‐hfbc) lanthanide(III) complexes with an encapsulated alkali metal and ammonium ions M[Ln((+)‐hfbc)4] (hereafter abbreviated as M‐Ln : (+)‐hfbc, (+)‐heptafluorobutyrylcamphorate; M, ammonium or benzyl ammonium ions as well as alkali metal ions) was reported and discussed. The electronic circular dichroism (CD) spectra in the intraligand π−π* transition of M–Ln were examined in view of the solvent effect. Here, the concentration, alkali metal, and ammonium ion dependences are compared with the solid CD, 5D0 ← 7F0(Eu(III)) excitation spectra, circularly polarized luminescence, and vibrational circular dichroism. It has been revealed that the dodecahedral eight coordinate DD‐8‐M‐Ln complexes in crystals are equilibrated between the diastereoselectively formed square antiprism eight coordinate SAPR‐8‐M‐Ln and [Ln((+)‐hfbc)3] in EtOH and CH3CN solutions or between the SAPR‐8‐M‐Ln and DD‐D2d(mmmm)‐8‐M‐Ln complexes in CHCl3 solution. The observed CD couplets are found to reflect the exciton CD couplets which are useful to determine the four‐bladed SAPR‐(llll) absolute configuration around the lanthanide(III) ion. Chirality 24:1055–1062, 2012. © 2012 Wiley Periodicals, Inc.
Advances in Targeting Voltage‐Gated Sodium Channels with Small Molecules
Authors: Nardi Antonio , Damann Nils , Hertrampf Torsten , Kless Achim 
Published: September 2012

AbstractBlockade of voltage‐gated sodium channels (VGSCs) has been used successfully in the clinic to enable control of pathological firing patterns that occur in conditions as diverse as chronic pain, epilepsy, and arrhythmias. Herein we review the state of the art in marketed sodium channel inhibitors, including a brief compendium of their binding sites and of the cellular and molecular biology of sodium channels. Despite the preferential action of this drug class toward over‐excited cells, which significantly limits potential undesired side effects on other cells, the need to develop a second generation of sodium channel inhibitors to overcome their critical clinical shortcomings is apparent. Current approaches in drug discovery to deliver novel and truly innovative sodium channel inhibitors is next presented by surveying the most recent medicinal chemistry breakthroughs in the field of small molecules and developments in automated patch‐clamp platforms. Various strategies aimed at identifying small molecules that target either particular isoforms of sodium channels involved in specific diseases or anomalous sodium channel currents, irrespective of the isoform by which they have been generated, are critically discussed and revised.
Identification of Drugs Inducing Phospholipidosis by Novel in vitro Data
Authors: Muehlbacher Markus , Tripal Philipp , Roas Florian , Kornhuber Johannes 
Published: September 2012

AbstractDrug‐induced phospholipidosis (PLD) is a lysosomal storage disorder characterized by the accumulation of phospholipids within the lysosome. This adverse drug effect can occur in various tissues and is suspected to impact cellular viability. Therefore, it is important to test chemical compounds for their potential to induce PLD during the drug design process. PLD has been reported to be a side effect of many commonly used drugs, especially those with cationic amphiphilic properties. To predict drug‐induced PLD in silico, we established a high‐throughput cell‐culture‐based method to quantitatively determine the induction of PLD by chemical compounds. Using this assay, we tested 297 drug‐like compounds at two different concentrations (2.5 μM and 5.0 μM). We were able to identify 28 previously unknown PLD‐inducing agents. Furthermore, our experimental results enabled the development of a binary classification model to predict PLD‐inducing agents based on their molecular properties. This random forest prediction system yields a bootstrapped validated accuracy of 86 %. PLD‐inducing agents overlap with those that target similar biological processes; a high degree of concordance with PLD‐inducing agents was identified for cationic amphiphilic compounds, small molecules that inhibit acid sphingomyelinase, compounds that cross the blood–brain barrier, and compounds that violate Lipinski’s rule of five. Furthermore, we were able to show that PLD‐inducing compounds applied in combination additively induce PLD.
Tackling Sample‐Related Artifacts in Membrane FCS Using Parallel SAF and UAF Detection
Authors: Winterflood Christian M. , Ruckstuhl Thomas , Reynolds Nicholas P. , Seeger Stefan 
Published: September 2012

AbstractThe complex shape and plasticity of cells is an intricate issue for the measurement of molecular diffusion in plasma membranes by fluorescence correlation spectroscopy (FCS). An important precondition for accurate diffusion measurements is a sufficient flatness of the membrane over the considered region and the absence of non‐membrane‐bound fluorescence diffusion. A method is presented to identify axial motion components caused by a non‐ideal geometry of the membrane based on simultaneous measurement of the fluorescence emitted above and below the critical angle of the specimen/glass interface. Thereby, two detection volumes are generated that are laterally coincident, but differ in their axial penetration of the specimen. The similarity between the intensity tracks of the supercritical angle fluorescence (SAF) and the undercritical angle fluorescence (UAF) strongly depends on the membrane flatness and intracellular fluorescence, and can help to avoid sample‐related artifacts in the diffusion measurement.
Enhancement of Iodine–Hydride Interaction by Substitution and Cooperative Effects in NCX–NCI–HMY Complexes
Authors: Li Qing‐Zhong , Sun Liang , Liu Xiao‐Feng , Li Wen‐Zuo , Cheng Jian‐Bo , Zeng Yan‐Li 
Published: September 2012

AbstractThe NCX‐NCI‐HMY (X=H, Cl, Br, I, Li; M=Be, Mg; Y=H, Li, Na) trimers are investigated to find ways to enhance the iodine–hydride interaction. The interaction energy in the NCI–HMH dimer is −2.87 and −5.87 kcal mol−1for M=Be and Mg, respectively. When the free H atom in the NCI–HMH dimer is replaced with an alkali atom, the interaction energy is enhanced greatly. When NCX is added into this dimer, the interaction energy of the iodine–hydride interaction is increased by 9–45 % and its increased percentage follows the order X=Cl<Br<H<I<Li and M=Be<Mg. The combination of the alkali substitution and the cooperativity results in a more prominent enhancing effect. The largest interaction energy is found for the NCLi–NCI–HMgLi trimer (−7.03 kcal mol−1). The influence of the I⋅⋅⋅H interaction on the X⋅⋅⋅N interaction is also studied in the trimers. Both types of interactions are analyzed with NBO, AIM, and MEP. The interaction energy in the trimer is also unveiled by a many‐body analysis.
Plasmonic Enhancement of a Photocycloreversion Reaction of a Diarylethene Derivative Using Individually Dispersed Silver Nanoparticles
Authors: Nishi Hiroyasu , Asahi Tsuyoshi , Kobatake Seiya 
Published: September 2012

AbstractThe fabrication of silver nanoparticles covered with polymers with a well‐defined core–shell structure and the quantitative evaluation of the plasmonic enhancement effect on a photochemical reaction in the vicinity of these silver nanoparticles individually dispersed in a medium are described. The photocycloreversion reaction of a diarylethene polymer in the vicinity of silver nanoparticles was enhanced by 2–6 times relative to the reaction without the nanoparticles. The promotion of the photocycloreversion reaction is due to enhancement of the electromagnetic field near the surface of the silver core.
Three Modes of Proton Transfer in One Chromophore: Photoinduced Tautomerization in 2‐(1H‐Pyrazol‐5‐yl)Pyridines, Their Dimers and Alcohol Complexes
Authors: Vetokhina Volha , Dobek Krzysztof , Kijak Michał , Kamińska Izabela I. , Muller Keven , Thiel Werner R. , Waluk Jacek , Herbich Jerzy 
Published: September 2012

AbstractStudies of 2‐(1H‐pyrazol‐5‐yl)pyridine (PPP) and its derivatives 2‐(4‐methyl‐1H‐pyrazol‐5‐yl)pyridine (MPP) and 2‐(3‐bromo‐1H‐pyrazol‐5‐yl)pyridine (BPP) by stationary and time‐resolved UV/Vis spectroscopic methods, and quantum chemical computations show that this class of compounds provides a rare example of molecules that exhibit three types of photoreactions: 1) excited‐state intramolecular proton transfer (ESIPT) in the syn form of MPP, 2) excited‐state intermolecular double‐proton transfer (ESDPT) in the dimers of PPP in nonpolar media, as well as 3) solvent‐assisted double‐proton transfer in hydrogen‐bonded 1:1 complexes of PPP and MPP with alcoholic partners. The excited‐state processes are manifested by the appearance of a dual luminescence and a bimodal irreversible kinetic coupling of the two fluorescence bands. Ground‐state syn–anti equilibria are detected and discussed. The fraction of the higher‐energy anti form varies for different derivatives and is strongly dependent on the solvent polarity and hydrogen‐bond donor or acceptor abilities.
Cognitive Bibliotherapy for Mild Depressive Symptomatology: Randomized Clinical Trial of Efficacy and Mechanisms of Change
Authors: Moldovan Ramona , Cobeanu Oana , David Daniel 
Published: September 2012

BackgroundIt has been increasingly recognized that subthreshold depression is associated with considerable personal, social and economic costs. However, there is no accepted definition or clear‐cut treatment for subthreshold depression. Cognitive bibliotherapy is a promising approach, but further research is necessary in order to assess its clinical efficacy and key mechanisms of change.AimThis study aimed to investigate the efficacy of bibliotherapy for subthreshold depression and test whether maladaptive cognitions mediate the effects of bibliotherapy on depressive symptoms.MethodA total of 96 young adults with subthreshold depression were randomized in one of the following treatment conditions: immediate treatment, delayed treatment, placebo and no treatment. The main outcome was represented by depressive symptoms assessed before, during and immediately after the treatment, as well as at 3‐month follow‐up. Automatic thoughts, dysfunctional attitudes and irrational beliefs were also assessed throughout the study, and we investigated their involvement as mediators of bibliotherapy effects on depressive symptoms.ResultsThe results indicated that cognitive bibliotherapy resulted in statistically and clinically significant changes both in depressive symptoms and cognitions, which were maintained at follow‐up. In contrast, placebo was only associated with a temporary decrease in depressive symptoms, without significant cognitive changes. No changes in symptoms or cognitions were found in the delayed treatment and no treatment groups. We also found that automatic thoughts significantly mediated the effect of bibliotherapy on depressive symptoms.ConclusionThis study provided compelling evidence for the efficacy of cognitive bibliotherapy in subthreshold depression and showed that changes in automatic thoughts mediated the effect of bibliotherapy on depressive symptoms. Copyright © 2012 John Wiley & Sons, Ltd.Key Practitioner Message

Cognitive bibliotherapy is an effective treatment of subthreshold depression.
Changing automatic thoughts is important, as they mediate the bibliotherapy effect on depressive symptoms.
Cognitive bibliotherapy is a potential alternative or adjunct to psychotherapy for mildly depressed adults.
Dislocation‐related photoluminescence imaging of mc‐Si wafers at room temperature
Authors: Mankovics D. , Schmid R. P. , Arguirov T. , Kittler M. 
Published: September 2012

AbstractWe report on a method for fast detection of defect rich areas in multicrystalline silicon solar wafers. It is based on photoluminescence imaging of the whole wafers and detects both the band‐to‐band radiation as well as the dislocation specific radiation D1. To illustrate the capabilities of the method we examined 5.0 × 5.0 cm2 wafer pieces in different stages of their processing. The achieved resolution of the D1 images was ∼120 μm, within a total recording time of 550 ms.
Controlling Surface Enrichment in Polymeric Hole Extraction Layers to Achieve High‐Efficiency Organic Photovoltaic Cells
Authors: Kim Dong‐Hun , Lim Kyung‐Geun , Park Jong Hyeok , Lee Tae‐Woo 
Published: September 2012

AbstractHole extraction in organic photovoltaic cells (OPVs) can be modulated by a surface‐enriched layer formed on top of the conducting polymer‐based hole extraction layer (HEL). This tunes the surface work function of the HEL to better align with the ionization potential of the polymeric photoactive layer. Results show noticeable improvement in device power conversion efficiencies (PCEs) in OPVs. We achieved a 6.1 % PCE from the OPV by optimizing the surface‐enriched layer.
Cramer–Rao bound based mean‐squared error and throughput analysis of superimposed pilots for semi‐blind multiple‐input multiple‐output wireless channel estimation
Authors: Jagannatham Aditya K. , Rao Bhaskar D. 
Published: September 2012

SUMMARYThis work presents a study of the mean‐squared error (MSE) and throughput performance of superimposed pilots (SP) for the estimation of a multiple‐input multiple‐output (MIMO) wireless channel. The Cramer–Rao bound (CRB) is derived for SP based estimation of the MIMO channel matrix. Employing the CRB analysis, it is proved that the asymptotic MSE bound is potentially 3 dB lower than the MSE performance of the existing SP mean based estimation (SPME) schemes. Motivated by this observation, a novel SP semi‐blind scheme is presented for MIMO channel estimation. This scheme asymptotically achieves the CRB and hence has a lower MSE of estimation when compared with SPME schemes. We also derive closed form expressions for the optimal source‐pilot power allocation in SP by maximizing the post‐processing signal‐to‐noise power ratio at the receiver. In the final part, a new result is presented for the worst‐case capacity of a communication channel with correlated information symbols and noise. This framework is employed to quantify the throughput performance of SP and also to demonstrate the bandwidth efficiency of SP compared with that of a conventional pilot based system. Copyright © 2012 John Wiley & Sons, Ltd.
Glycerol hydrogenolysis into propanediols using in situ generated hydrogen – A critical review
Authors: Martin Andreas , Armbruster Udo , Gandarias Inaki , Arias Pedro Luis 
Published: September 2012

AbstractThe rise in chemical transesterification of plant triglycerides towards biodiesel is unbowed and thus the available amount of glycerol is still increasing. The produced amount overruns the chemically used portion. Various ways to convert glycerol have been shown recently to yield attractive intermediates and final products. One of the options of future chemical utilisation of glycerol might be its conversion to propanediols (1,2‐PDO (propylene glycol), 1,3‐PDO (trimethylene glycol)) by hydrogenolysis. 1,2‐PDO finds various applications in chemical industries; 1,3‐PDO is mainly used for the manufacture of polymers. A synthesis route via glycerol might substitute present industrial syntheses using for example propylene oxide. Such an alternative synthesis route might run in the presence of externally fed hydrogen or by use of in situ generated hydrogen that can be supplied for example by glycerol aqueous phase reforming (APR) and/or catalytic transfer hydrogenation (CTH) using hydrogen donor molecules. A very attractive approach seems to be the use of formic acid as hydrogen donor for CTH because only carbon dioxide is liberated as a by‐product. This paper summarises most significant reports of the last decade, dealing with the production of PDOs via glycerol hydrogenolysis by in situ generated hydrogen.
Electrophilic Cyclization and Ring‐Closing Metathesis as Key Steps in the Synthesis of a 12‐Membered Cyclic Enediyne
Authors: Danilkina Natalia , Nieger Martin , Selivanov Stanislav , Bräse Stefan , Balova Irina 
Published: September 2012

AbstractFor the first time, electrophilic cyclization and ring‐closing metathesis were used as key steps in the synthesis of a macrocyclic enediyne system, which allowed a 12‐membered dienediyne containing a thiophene‐fused ring to be obtained. The macrocycle synthesized represents a class of compounds that possess planar chirality and exists in the solid state as two enantiomers, whereas in solution the rate of interconversion is rapid as a result of unhindered switching of the double bond through the macrocycle.
Nickel‐Catalyzed Indium(I)‐Mediated syn‐Selective Propargylation of Aldehydes
Authors: Hirashita Tsunehisa , Suzuki Yuuki , Tsuji Hiromitsu , Sato Yoshiki , Naito Kojiro , Araki Shuki 
Published: September 2012

AbstractLow‐valent indium(I)‐mediated nickel‐catalyzed propargylation of aldehydes is described. The nickel/indium(I)‐mediated reaction of propargylic carbonates possessing different substitution patterns afforded syn‐homopropargylic alcohols in high yields upon coupling with a variety of carbonyl compounds. Both the nickel catalyst and the phosphane ligands were found to play a crucial role in this transformation. The diastereoselectivity is strongly dependent on the ligand employed. A mechanism involving umpolung of the propargylnickel intermediates under the influence of low‐valent indium is proposed to account for the dependence of the stereochemical characteristics of the phosphane ligands.
Enhancement of Electrochemiluminescence of Porous Silicon with Tri‐n‐propylamine as Co‐reactant
Authors: Mo Yan , Li Fucheng , Zheng Baozhan , Yang Suolong , Yuan Hongyan , Guo Yong , Xiao Dan 
Published: September 2012

AbstractVisible light emission can be stimulated by applying a cyclic bias to a porous silicon/tri‐n‐propylamine (PS/TPrA) solid/liquid system. With the presence of 2.5 mM TPrA, the electrochemiluminescence intensity of the in situ formed PS electrode is 450 times higher than the blank solution. An applied voltage as low as 1.2 V is capable of generating light emission, indicating that current‐induced chemical reactions are an aid to the generation of charge carriers. A mechanism involving oxidation of TPrA followed by hole injection is proposed. The system also shows good ECL stability. In addition, the ECL emission can be inhibited by diphenols rather than phenol.
A Novel Process for the Fabrication of a Silver‐Nanoparticle‐Modified Electrode and Its Application in Nonenzymatic Glucose Sensing
Authors: Jia Mingzhe , Wang Tong , Liang Fenfen , Hu Jingbo 
Published: September 2012

AbstractIn this work, we present a novel process for fabrication of a silver‐nanoparticle‐modified electrode using silver ion implantation. This method is facile, low‐cost and environmental friendly without the use of any other chemicals. The obtained AgNPs on the electrode surface, which were free from any reagents surrounding or binding to them, showed prominent electrocatalytic activity towards the oxidation of glucose, leading to a nonenzymatic glucose sensor with a wide linear range and a detection limit of 0.5 µM. In addition, the modified electrode also exhibited acceptable reproducibility and long‐term stability.
Energy Dispersive X‐ray Diffraction Applied to Laboratory Investigation on Proton Exchange Membrane Water Content in Working Fuel Cells
Authors: Isopo A. , Nobili F. , Rossi Albertini V. 
Published: September 2012

AbstractAn original method, based on the energy‐dispersive X‐ray diffraction, has been recently proposed as a possible laboratory tool to accomplish long time resolved investigation of the water content in a proton exchange membrane fuel cell.However, this method has never been applied to a real working fuel cell. Therefore, a clear comprehension of its effectiveness in terms of relevant parameters such as time and space resolution, sensitivity, and reproducibility has not yet been achieved. In this paper, all these aspects are discussed and clarified.In order to focus on the method overall effectiveness and on the extent of possible improvements, a basic experimental configuration for both the electrochemical station and the X‐ray equipment has been set.The method is described with particular attention to its operating principle and to the evaluation of the errors introduced in data assessment. Finally, applications to some model experiments, in particular working states of the device, are provided and the obtained results are discussed.
Barodesy as a novel hypoplastic constitutive theory based on the asymptotic behaviour of sand
Authors: Kolymbas Dimitrios 
Published: September 2012

AbstractA new type constitutive equation of the rate type T̊ = h(T,D,e) for granular materials is introduced in the frame of Rational Mechanics. This new approach to constitutive modelling, called “barodesy”, is based on the asymptotic behaviour of sand. Barodesy can be seen as a further development of hypoplasticity. Despite its striking mathematical simplicity, it captures many aspects of sand behaviour.Barodesie als eine neue hypoplastische Stofftheorie auf der Grundlage des asymptotischen Verhaltens von Sand. Es wird eine konstitutive Gleichung vom Ratentyp T̊ = h(T,D,e) für granulare Stoffe im Rahmen der sog. Rational Mechanics eingeführt. Diese neue Betrachtung von Stoffmodellen, genannt “Barodesie”, beruht auf das asymptotische Verhalten von Sand und kann als eine Weiterentwicklung der Hypoplastizität betrachtet werden. Trotz der auffälligen mathematischen Einfachheit, kann sie viele Aspekte des Verhaltens von Sand beschreiben.
Surgical margins in head and neck cancer: A contemporary review
Authors: Hinni Michael L. , Ferlito Alfio , Brandwein‐Gensler Margaret S. , Takes Robert P. , Silver Carl E. , Westra William H. , Seethala Raja R. , Rodrigo Juan P. , Corry June , Bradford Carol R. , Hunt Jennifer L. , Strojan Primož , Devaney Kenneth O. , Gnepp Douglas R. , Hartl Dana M. , Kowalski Luiz P. , Rinaldo Alessandra , Barnes Leon 
Published: September 2012

AbstractAdequate resection margins are critical to the treatment decisions and prognosis of patients with head and neck squamous cell carcinoma (HNSCC). However, there are numerous controversies regarding reporting and interpretation of the status of resection margins. Fundamental issues relating to the basic definition of margin adequacy, uniform reporting standards for margins, optimal method of specimen dissection, and the role of intraoperative frozen section evaluation, all require further clarification and standardization. Future horizons for margin surveillance offer the possible use of novel methods such as “molecular margins” and contact microscopic endoscopy, However, the limitations of these approaches need to be understood. The goal of this review was to evaluate these issues to define a more rational, standardized approach for achieving resection margin adequacy for patients with HNSCC undergoing curative resection. © 2012 Wiley Periodicals, Inc. Head Neck, 2013