bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enantioselective Epoxidation of Styrene by Manganese Chiral Schiff Base Complexes Immobilized on MCM‐41
Authors: Mandal Moon , Nagaraju Vemu , Sarma Bipul , Karunakar G. V. , Bania Kusum K. 
Published: February 2015

AbstractTwo chiral MnIII complexes synthesized and characterized by single‐crystal X‐ray diffraction were grafted onto mesoporous silica MCM‐41. The MCM‐41‐immobilized solid chiral catalysts were characterized by various spectrochemical and physicochemical methods (XRD, FTIR, 29Si NMR, TGA, UV/Vis/DRS, EPR, cyclic voltammetry, SEM, BET). Both the homogeneous and heterogeneous MnIII chiral complexes are found to be effective catalysts for epoxidation of styrene. MCM‐41‐supported chiral catalysts are found to retain their catalytic activity up to five cycles. When an ionic liquid was implemented to enhance the catalytic recyclability of the homogeneous catalysts, they can be recycled up to three times. However, after the third cycle the catalytic activities of the complexes were found to decrease due to rupturing of the chiral catalyst.
Service‐oriented 5G network architecture: an end‐to‐end software defining approach
Authors: Yang Mao , Li Yong , Li Bo , Jin Depeng , Chen Sheng 
Published: February 2015

SummaryWith the ever‐increasing mobile demands and proliferation of mobile services, mobile Internet has penetrated into every aspect of human life. Although the 4G mobile communication system is now being deployed worldwide, simply evolving or incrementally improving the current mobile networks can no longer keep the pace with the proliferation of mobile services. Against this background, aiming to achieve service‐oriented 5G mobile networks, this article proposes an end‐to‐end software defining architecture, which introduces a logically centralized control plane and dramatically simplifies the data‐plane. The control plane decomposes the diversified mobile service requirements and, correspondingly, controls the functions and behaviors of data‐plane devices. Consequently, the network directly orients towards services, and the devices are dynamically operated according to the service requirements. Therefore, the proposed architecture efficiently guarantees the end‐to‐end QoS and quality of experience. The challenges and key technologies of our architecture are also discussed in this article. Real traces‐based simulations validate the performance advantages of proposed architecture, including energy efficiency and the whole performance. Copyright © 2015 John Wiley & Sons, Ltd.
Coordinative Flexibility of a Thiophenolate Oxazoline Ligand in Nickel(II), Palladium(II), and Platinum(II) Complexes
Authors: Peschel Lydia M. , Holzer Christof , Mihajlović‐Lalić Ljiljana , Belaj Ferdinand , Mösch‐Zanetti Nadia C. 
Published: February 2015

AbstractThe synthesis, full characterization, and molecular structures of seven new coordination compounds that feature the 2‐(4′,4′‐dimethyloxazolin‐2′‐yl)thiophenolate ligand (S‐Phoz) with group 10 metals Ni, Pd, and Pt in the +II oxidation state are presented. The ML2 complexes [Pt(S‐Phoz)2] (1a), [Pd(S‐Phoz)2] (1b), and [Ni(S‐Phoz)2] (2) were prepared starting from MCl2. Compound 1a was obtained isomerically pure in a trans arrangement, whereas its Pd analogue 1b exhibits a dynamic, solvent‐dependent cis/trans equilibrium, and 2 adopts a tetrahedral arrangement. The reaction of LiS‐Phoz with [cis‐MCl2(PPh3)2] precursors resulted in full replacement of the PPh3 for M = Ni and in partial substitution for M = Pt, Pd to yield [Ni(S‐Phoz)2] (2), [Pt(κ2‐S‐Phoz)(κ1‐S‐Phoz)(PPh3)] (3a), and [Pd(κ2‐S‐Phoz)(κ1‐S‐Phoz)(PPh3)] (3b). The Pd compound 3b exhibits an interesting solvent‐dependent equilibrium with 1b and PPh3 as demonstrated by 1H and 31P NMR spectroscopy. Compounds [{PdCl(S‐Phoz)}2] (4) and [PdCl(S‐Phoz)(PPh3)] (5) were synthesized from [PdCl2(NCMe)2]. Molecular structures of compounds trans‐1a, trans‐1b, 2, 3a, 3b, 4, and 5 were determined by single‐crystal X‐ray diffraction studies. With the exception of the Ni complex 2, all compounds exhibit distorted square‐planar geometries.
Electronic Structures of “Low‐Valent” Neutral Complexes [NiL2]0 (S = 0; L = bpy, phen, tpy) – An Experimental and DFT Computational Study
Authors: Wang Mei , England Jason , Weyhermüller Thomas , Wieghardt Karl 
Published: February 2015

AbstractThe electronic structures of the neutral complexes [Ni(bpy)2]0, [Ni(tpy)2]0, and [Ni(phen)2]0 (bpy = 2,2′‐bipyridine; tpy = 2,2′:6′,2″‐terpyridine; phen = 1,10‐phenanthroline) have been investigated by a combination of UV/Vis spectroscopy, magnetochemistry, and X‐ray crystallography {the structures of [Ni(bpy)2]0, [Ni(tpy)Cl]0, [Cu(bpy)2](PF6)2 (reinvestigation), and [(bpy)2Cu(μ2‐NO3)Cu(bpy)2](PF6)3 are reported herein}. To further clarify the electronic structures of the title compounds and elucidate those of the electron transfer series produced by their reduction and oxidation, broken‐symmetry (BS) density functional theory (DFT) calculations were performed for [Ni(bpy)2]m (m = 2+, 1+, 0, 1–, 2–), [Ni(bpy)3]m (m = 3+, 2+, 1+, 0, 1–, 2–), [Ni(tpy)2]m (m = 3+, 2+, 1+, 0), and, for calibration purposes, [Zn(phen)(NH3)xCl(2–x)]0 (x = 2, 1, 0). Through the aforementioned studies, it was shown that none of the so called “low‐valent” Ni complexes contain zero‐valent Ni. Instead, they each contain at least one (bpy·)1–, (tpy·)1–, or (phen·)1– π‐radical monoanionic ligand. More specifically, they are all four‐coordinate and possess the following electronic structures: [NiI(bpy·)(bpy0)] (delocalized), [NiI(tpy·)(tpy0)] (delocalized), and [NiII(Mephen·)2] (Mephen = 2,9‐dimethyl‐1,10‐phenanthroline). In addition, all members of the series [Ni(bpy)2]m with m ≤ 1+ contain a NiI ion (d9, SNi = 1/2), and the redox processes that link them are ligand‐centered. A similar finding was made for six‐coordinate [Ni(bpy)3]m and [Ni(tpy)2]m, but in this case complexes with m ≤ 2+ contain Ni ions posessing an invariant +II oxidation state (d8, SNi = 1).
Suzuki Coupling Reactions Catalyzed with Palladacycles and Palladium(II) Complexes of 2‐Thiophenemethylamine‐Based Schiff Bases: Examples of Divergent Pathways for the Same Ligand
Authors: Joshi Hemant , Prakash Om , Sharma Alpesh K. , Sharma Kamal Nayan , Singh Ajai K. 
Published: February 2015

AbstractActivation of Suzuki coupling with a complex of palladium varies with the mode of coordination of its ligand. The moisture‐/air‐insensitive palladacycles and palladium complexes designed using the same ligand (Schiff base, coordinating as an N,C– and N,O– ligand, respectively) have been found to follow different pathways. Palladacycles are more efficient, as their 0.001 mol‐% loading gives good conversion (yield > 90 %) in several cases. Higher loading than this is required for Pd complexes to obtain a similar yield. Activation with palladacycles involves the role of nanosized Pd‐containing species generated in situ during catalysis, in which, as with PdII complexes, no such particle is formed and Pd0 probably remains protected by the sulfur of the thienyl group. The Schiff bases used here were designed by the reaction of 2‐thiophenemethylamine with 2‐hydroxybenzophenone/2‐hydroxy‐4‐methoxybenzophenone/2‐hydroxyacetophenone (L1/L2/L3). Upon treatment with [PdCl2(CH3CN)2] and [Na2PdCl4] they gave palladacycles [PdL1/L2(CH3CN)Cl] (1/3) and palladium(II) complexes [Pd(L1/L2/L3)2] (2/4/5), respectively. Compounds L1–L3 and their complexes 1–5 were authenticated with 1H and 13C{1H} NMR spectroscopy, and HRMS. Single crystal structures of 1, 2, 4, and 5 reveal nearly square‐planar geometry around Pd in each case. The PPh3/Hg poisoning and two‐phase tests indicate that the catalysis is homogeneous for both the palladacycle and palladium complexes, probably through leaching of Pd0 from NPs in the case of the former.
Synthesis of the First Example of Selenium‐Containing Platinum(II)–Alkenylarylalkynyl Complexes
Authors: Rahman Md. Mostafizur , Younus Muhammad , Ogawa Akiya 
Published: February 2015

AbstractA synthetic method has been developed to construct a new series of selenium‐containing trans‐platinum(II)–bis(alkenylarylalkynyl) complexes with general formula trans‐[(PR3)2Pt{C≡C–Ar–C(SePh)=CH(SePh)}2] (R = ethyl, phenyl, and Ar = phenylene, biphenylene), having two phenylseleno moieties on each alkenyl backbone. Reaction of the diterminal alkynyl ligand of trans‐platinum(II)–bis(alkynylarylalkynyl) complex 1 with an amount slightly in excess of two equivalents of diphenyl diselenide in chloroform readily affords trans‐platinum(II) complex 2 upon irradiation, in good to excellent yields with good regioselectivity. As compared to the absorption band of platinum(II) complexes 1, it was found that the position of the lowest energy absorption bands of platinum(II) complexes 2 are redshifted.
Asymmetric Base‐Free Michael Addition at Room Temperature with Nickel‐Based Bifunctional Amido‐Functionalized N‐Heterocyclic Carbene Catalysts
Authors: Rao Mitta Nageswar , Haridas Meera , Gangwar Manoj Kumar , Rajakannu Palanisamy , Kalita Alok Ch. , Ghosh Prasenjit 
Published: February 2015

AbstractA series of nickel‐based chiral bifunctional catalysts (1d–3d) with N‐heterocyclic carbene (NHC) ligands derived from (1R)‐(–)‐menthol, (1S)‐(–)pinene, and (1R)‐(+)‐camphor have been successfully designed for asymmetric Michael addition reactions under base‐free conditions. The NHC complexes, namely, [1‐R‐3‐{N‐(phenylacetamido)}imidazol‐2‐ylidene]2Ni [R = (1S)‐menthyl (1d), (1S)‐pinane (2d), and (1R)‐isobornyl (3d)], bearing chiral ancillaries on the amido‐functionalized side arms of the NHC ligands, performed the bifunctional catalysis of the asymmetric base‐free Michael addition reaction of the α‐methyl cyano ester substrates ethyl 2‐cyanopropanoate (4), isopropyl 2‐cyanopropanoate (5), and tert‐butyl 2‐cyanopropanoate (6) with the activated olefinic substrates methyl vinyl ketone (7) and acrylonitrile (8) in 63–98 % yields with enantiomeric excess (ee) values of 2–75 % at room temperature in 8 h. More interestingly, only the longest of the three catalysts, the menthol derivative 1d, showed significant chiral induction of up to 75 % ee; this has been attributed to the reduction of the steric influence owing to the relatively distant dispositions of the chiral ancillaries from the catalytically active metal center that arise as a consequence of the cis geometries of 1d–3d.
Synthesis of 2‐Acylphenol and Flavene Derivatives from the Ruthenium‐Catalyzed Oxidative C–H Acylation of Phenols with Aldehydes
Authors: Lee Hanbin , Yi Chae S. 
Published: February 2015

AbstractThe cationic ruthenium hydride complex [(C6H6)(PCy3)(CO)RuH]+BF4– has been found to be an effective catalyst for the oxidative C–H coupling reaction of phenols with aldehydes to give 2‐acylphenol compounds. The coupling of phenols with α,β‐unsaturated aldehydes selectively gives the flavene derivatives. The catalytic method mediates direct oxidative C–H coupling of phenol and aldehyde substrates without using any metal oxidants or forming wasteful byproducts.
Superhard, Antireflective Texturized Coatings Based on Hyperbranched Polymer Composite Hybrids for Thin‐Film Solar Cell Encapsulation
Authors: González Lazo Marina A. , Schüler Andreas , Haug Franz‐Josef , Ballif Christophe , Månson Jan‐Anders E. , Leterrier Yves 
Published: February 2015

AbstractIn this study, we demonstrate by simulation and experiment the antireflective (AR) performance of hyperbranched polymer (HBP) nanocomposites textures replicated from a moth‐eye pattern using ultraviolet (UV) nanoimprint lithography. A UV‐curable acrylated HBP and a hybrid composite of the HBP with silica nanoparticles with an organometal precursor were used. Using effective medium theory (EMT) simulations, optimal patterns were found to be arrays of paraboloids with stable AR performance over a large range of geometries. A good agreement was found between the simulated and measured optical behavior of such AR arrays with a normal reflectance within the visible range of approximately 4 % for the use of a glass substrate. The photocurrent of AR‐coated a‐Si:H solar cells was found to be 2 % higher than the reference value of an uncoated cell whereas, for AR‐coated tandem thin film Si cells, the increase was 3 % for the top a‐Si:H cell and 2 % for the bottom microcrystalline Si cell.
Lowest‐density MDS array codes for reliable Smart Meter networks
Authors: Sandell Magnus , Tosato Filippo 
Published: February 2015

AbstractIn this paper, we introduce a lowest‐density maximum‐distance separable (MDS) array code, which is applied to a Smart Meter network to introduce reliability. By treating the network as distributed storage with multiple sources, information can be exchanged between the nodes in the network allowing each node to store parity symbols relating to data from other nodes. A lowest‐density MDS array code is then applied to make the network robust against outages, ensuring low overhead and data transfers. We show the minimum amount of overhead required to be able to recover from r node erasures in an n node network and explicitly design an optimal array code with lowest density. In contrast to existing codes, this one has no restrictions on the number of nodes or erasures it can correct. Furthermore, we consider incomplete networks where all nodes are not connected to each other. This limits the exchange of data for purposes of redundancy, and we derive conditions on the minimum node degree that allow lowest‐density MDS codes to exist. We also present an explicit code design for incomplete networks that is capable of correcting two node failures. Copyright © 2015 John Wiley & Sons, Ltd.
New insights into the neural network mediating reading processes provided by cortico‐subcortical electrical mapping
Authors: Zemmoura Ilyess , Herbet Guillaume , Moritz‐Gasser Sylvie , Duffau Hugues 
Published: February 2015

AbstractObjectivesTo ascertain the neural network mediating reading using intraoperative electrostimulation.Experimental designA cortical and axonal intraoperative electrical mapping of reading processes was achieved in seven patients who underwent awake surgery for a left occipitotemporal glioma. We performed resection cavity overlapping and superimposition with a diffusion tensor imaging‐based white matter atlas. We assessed the relationship between the location of resection cavities and the occurrence of reading impairments of regular, irregular, and pseudowords.Principal observationsIntraoperative stimulation of the left posterior inferior temporal cortex (ITCp) elicited reading disturbances. Subcortical stimulation at the anterior portion of the visual word form area (VWFA) induced addressed phonology (irregular words reading) disturbances. Subcortical stimulation of the connection between VWFA and the posterior segment of the arcuate fascicle (AFp) induced both addressed and assembled phonology (irregular and pseudowords reading) disturbances. Postoperative assessment showed that resection of the posterior portion of the inferior longitudinal fascicle (ILFp), connecting the visual cortex to VWFA, induced long‐term and global reading impairment. Resection of the terminations of left AFp in the ITCp‐induced irregular and pseudowords reading disturbances with no impairment of regular words reading. Resection of the anterior portion of ILF did not induce reading impairment.ConclusionsOur data support an inner posterior‐to‐anterior hierarchical coding of letter strings in the VWFA and a crucial role of the left ILFp to provide visual inputs to the VWFA. Furthermore, we suggest that the AFp is involved in an interactive feedback system between visual and nonvisual information, recruited when reading irregular and pseudowords. Hum Brain Mapp 36:2215–2230, 2015. © 2015 Wiley Periodicals, Inc.
A cortical–subcortical syntax pathway linking Broca's area and the striatum
Authors: Teichmann Marc , Rosso Charlotte , Martini Jean‐Baptiste , Bloch Isabelle , Brugières Pierre , Duffau Hugues , Lehéricy Stéphane , Bachoud‐Lévi Anne‐Catherine 
Published: February 2015

AbstractCombinatorial syntax has been shown to be underpinned by cortical key regions such as Broca's area and temporal cortices, and by subcortical structures such as the striatum. The cortical regions are connected via several cortico‐to‐cortical tracts impacting syntactic processing (e.g., the arcuate) but it remains unclear whether and how the striatum can be integrated into this cortex‐centered syntax network. Here, we used a systematic stepwise approach to investigate the existence and syntactic function of an additional deep Broca‐striatum pathway. We first asked 15 healthy controls and 12 patients with frontal/striatal lesions to perform three syntax tests. The results obtained were subjected to voxel‐based lesion‐symptom mapping (VLSM) to provide an anatomo‐functional approximation of the pathway. The significant VLSM clusters were then overlapped with the probability maps of four cortico‐cortical language tracts generated for 12 healthy participants (arcuate, extreme capsule fiber system, uncinate, aslant), including a probabilistic Broca‐striatum tract. Finally, we carried out quantitative analyses of the relationship between the lesion load along the tracts and syntactic processing, by calculating tract‐lesion overlap for each patient and analyzing the correlation with syntactic data. Our findings revealed a Broca‐striatum tract linking BA45 with the left caudate head and overlapping with VLSM voxel clusters relating to complex syntax. The lesion load values for this tract were correlated with complex syntax scores, whereas no such correlation was observed for the other tracts. These results extend current syntax‐network models, by adding a deep “Broca‐caudate pathway,” and are consistent with functional accounts of frontostriatal circuits. Hum Brain Mapp 36:2270–2283, 2015. © 2015 Wiley Periodicals, Inc.
Serum Adenosine Deaminase (ADA) Activity: A Novel Screening Test to Differentiate HIV Monoinfection From HIV‐HBV and HIV‐HCV Coinfections
Authors: Abdi Mohammad , Rahbari Rizgar , Khatooni Zahed , Naseri Nima , Najafi Adel , Khodadadi Iraj 
Published: February 2015

BackgroundCD4+ cell count, the common HIV infection screening test, is costly and unable to differentiate HIV monoinfection from its concurrent infection with hepatitis B or C virus. We aimed to ascertain diagnostic value of serum adenosine deaminase (ADA) activity as a useful tool to differentiate HIV mono‐ and co‐infection.MethodsBlood samples were collected from 30 HIV‐HBV and 30 HIV‐HCV coinfected patients, 33 HIV positive subjects, and 72 controls. CD4+ cell count, serum total ADA (tADA), and ADA1, and ADA2 isoenzyme activities were determined and their sensitivity and specificity were computed.ResultstADA and ADA2 activities were significantly higher and CD4+ counts were markedly lower in all patients compared with controls. Strong inverse agreements between CD4+ cell counts and both tADA and ADA2 activities were observed. Serum tADA and ADA1 activities showed the highest specificity and the highest sensitivity, respectively, for differentiating HIV monoinfection from HIV‐HBV and HIV‐HCV coinfections.ConclusionsWe showed strong agreement and correlation between CD4+ cell count and ADA enzyme activity. Based on high ADA sensitivity and specificity, it is concluded that determination of ADA activity might be a novel diagnostic tool to distinguish of HIV monoinfection from its coinfection with HBV or HCV.
Economic impact of considering El Niño‐Southern Oscillation on the representation of streamflow in an electric system simulator
Authors: Maciel Fernanda , Terra Rafael , Chaer Ruben 
Published: February 2015

ABSTRACTThe Electric Power System Simulator (SimSEE) is a model that optimizes and simulates the operation of an electric system and has been widely used to analyze the integrated power system in Uruguay. Among the stochastic processes that SimSEE needs to represent are the streamflow inputs to the hydroelectric dams, which constitute a key factor for both energy dispatches and mid‐term planning. A dominant feature of streamflow time series is that they show very high interannual variability, which represents a major uncertainty for energy operation in Uruguay. Part of this variability is associated with El Niño‐Southern Oscillation (ENSO) phenomena. In this work, a climate index associated with ENSO is incorporated to the stochastic generator of streamflow series used by the SimSEE. Forty six‐month‐long simulations are performed with and without such modifications. We find that the system operator can take advantage of the ENSO‐related information incorporated to SinSEE in 65% of the cases (semesters) considered, reducing the total costs of operation. This result still holds in a scenario with larger firm capacity. The amounts saved, however, are reduced as the firm capacity increases. The enhanced generation options associated with a larger firm capacity diminish the overall costs of generation, especially in times of low streamflow, rendering the savings associated with a more efficient management of the reservoir less significant.
Climatology of global lightning classified by stroke energy using WWLLN data
Authors: Iwasaki Hiroyuki 
Published: February 2015

ABSTRACTClimatological features of lightning, based on stroke energy, were studied by considering the hourly detection efficiency of the World Wide Lightning Location Network (WWLLN) data set from April 2009 to April 2014. Five regions were found in which the ratio of strong lightning (>90th percentile of stroke energy) to overall lightning exceeded 30% (high S‐ratio regions), and one region was determined in which the ratio of weak lightning (<10th percentile) to overall lightning exceeded 30% (high W‐ratio region). One region of high S‐ratio was the Tibetan Plateau. Lightning activity and the S‐ratio in this region increased during summer afternoons as rainfall increased; however, the large S‐ratio was observed in the grid where lightning activity was very weak. The four other areas of high S‐ratio were located over the ocean in the sub‐polar climatic zones of the Northern and Southern Hemispheres. In cold seasons of the two hemispheres, when rainfall amount increased, both the lightning activity and the S‐ratio increased, displaying nocturnal maxima; however, the amount of rainfall did not exhibit diurnal variation. Here, a large S‐ratio was also observed in the grid where lightning activity was very weak. Weak lightning activity dominated in the East Pacific. The activity of weak lightning and the W‐ratio showed a tendency to increase during daytime in the cold season. The seasonal variation of the W‐ratio was almost in accordance with rainfall amount; however, diurnal variation of the W‐ratio was not. A large value of the W‐ratio was also observed in the grid where the lightning activity was very weak.
Infrared Spectroscopic Evidence for a Heterogeneous Reaction between Ozone and Sodium Oleate at the Gas–Aerosol Interface: Effect of Relative Humidity
Authors: Nájera Juan J. , Percival Carl J. , Horn Andrew B. 
Published: February 2015

ABSTRACTThe heterogeneous ozonolysis of sodium oleate aerosols in an aerosol flow tube is reported under different relative humidity (RH%) conditions. Submicron sodium oleate particles were exposed to a known ozone concentration and the consumption of sodium oleate was monitored by infrared spectroscopy. When the experimental results are treated as a surface‐mediated reaction (i.e., following a Langmuir–Hinshelwood type mechanism), the following parameters are obtained: at low RH%, = (3 ± 1) × 10−16 cm3 molecule−1 and = (0.046 ± 0.006) s−1; at high RH%, = (6 ± 2) × 10−16 cm3 molecule−1 and = (0.21 ± 0.05) s−1. From these pseudo–first‐order coefficients, the reactive uptake coefficients for dry and aqueous sodium oleate aerosols are calculated as (1.5 − 0.5) × 10−7 and (1.7 − 0.7) × 10−6, respectively. Hydrated oleate aerosols display both an increase in the ozone trapping ability and an increase in the effective rate reaction at the droplet surface compared to dry aerosol surfaces. These observations may provide an explanation for some of the variability observed between lab studies of dry ozonolysis and real‐world, atmospheric lifetimes of oleic acid–related species.