bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cardiac rhythm abnormalities during intravenous immunoglobulin G(IVIG) infusion in two newborn infants: coincidence or association?
Authors: Tufekci Sinan , Coban Asuman , Bor Meltem , Yasa Beril , Nisli Kemal , Ince Zeynep 
Published: July 2015

Key Clinical MessageWe report the occurrence of supraventricular tachycardia during intravenous immunoglobulin (IVIG) infusion. Supraventricular tachycardia was observed in two newborn patients during IVIG infusion. Both of the babies responded to adenosine treatment. Cardiorespiratory monitoring during IVIG infusion can be recommended because of the possibility of this potentially lifethreatening adverse effect.
Synthesis and Peroxidase‐Like Activity of Cobalt@Carbon‐Dots Hybrid Material
Authors: Guo Yali , Liu Xiaoyu , Yang Chengduan , Wang Xudong , Wang Dan , Iqbal Anam , Liu Weisheng , Qin Wenwu 
Published: July 2015

AbstractA cobalt@carbon‐dots (Co@C‐dots) hybrid material is successfully prepared and well characterized. The hybrid material exhibits intrinsic peroxidase‐like activity and can be utilized for the degradation of methylene blue; it shows enhanced catalytic activities compared with bare Co nanoparticles or C‐dots. The good catalytic performance of the hybrid material may be attributed to synergistic effects between the Co nanoparticles and C‐dots. Furthermore, the catalytic mechanism of the Co@C‐dots hybrid material is also studied by using steady‐state and time‐resolved fluorometric analysis, which reveals that Co@C‐dots can effectively decompose H2O2 to produce reactive hydroxyl radicals (.OH). These results suggest that the Co@C‐dots hybrid material could be a promising material applied for biochemical analysis and water treatment.
Mesoporous Biphasic C and N Codoped Anatase Nanocrystal–Carbon Composites and their Derived Doped Anatase Nanoparticles in Phenol Elimination under Visible Light
Authors: Zhu Xiaojuan , Wei Wei , Wan Ying 
Published: July 2015

AbstractMesoporous C and N codoped anatase nanocrystal–carbon composites have been synthesized by chelation‐assisted coassembly of urea, TiCl4, resols, and triblock copolymer. The composite catalysts have biphasic constituents in the pore walls of amorphous carbon and C,N‐codoped anatase nanoparticles (≈4.0 nm) that are “glued” together; the composite catalysts also have open mesopores with high surface areas (≈340 m2 g−1), large pore volumes (≈0.20 cm3 g−1), and uniform pore sizes (≈5.0 nm). Upon calcination in air at 350 °C, the main‐group‐elements‐codoped anatase nanoparticles with a size of 4.3 nm can be obtained. The C,N‐codoped anatase nanoparticles feature a clear redshift absorption towards the visible‐light region and exhibit remarkable degradation efficiency for phenol. A repeated accumulation–photodegradation process is adopted to remove high concentrations of phenol (100 mg L−1) from water, thereby avoiding the use of organic solvent and the posttreatment of the catalyst. After six cycles, phenol is almost completely degraded. The features of the two constituents of the composite are discussed. The mesoporous carbon support shows a high adsorption capacity for phenol, which accumulates inside its pores, and the main‐group‐elements‐doped anatase nanoparticles can be well accessible to phenol, which it mineralizes under artificial visible light. Simultaneously, the “glue” role of the amorphous carbon can overcome the disadvantages of possible particle aggregation during processes and allow the catalyst to be reused.
Effect of NiAl2O4 Formation on Ni/Al2O3 Stability during Dry Reforming of Methane
Authors: Zhou Lu , Li Lidong , Wei Nini , Li Jun , Basset Jean‐Marie 
Published: July 2015

AbstractA series of alumina‐supported Ni catalysts were prepared to examine their activity and carbon deposition during dry reforming of methane (DRM). With an increase in the final calcination temperature to T=900 °C to form exclusively NiAl2O4, a catalyst with strong metal–support interactions was obtained. During a long‐term DRM reaction (of about t=100 h) at T=700 °C and with CH4/CO2=1:1, reduced Ni (from NiAl2O4) showed a high resistance to sintering and coking. The DRM kinetics behaviors of the catalysts calcined at different temperatures were also investigated. Carbon growth models were proposed to rationalize the different carbon morphologies observed on the catalysts.
DFT Mechanistic Investigation of the Gold(I)‐Catalyzed Synthesis of Azepino[1,2‐a]indoles
Authors: Giacinto Pietro , Cera Gianpiero , Bottoni Andrea , Bandini Marco , Miscione Gian Pietro 
Published: July 2015

AbstractWe describe a computational DFT investigation on the mechanism of the one‐pot synthesis of azepino‐indoles catalyzed by [Au(IPr)Cl]/AgOTf (IPr=1,3‐bis(2,6‐diisopropylphenyl‐imidazol‐2‐ylidene) by the simultaneous construction of the pyrrolyl and seven‐membered rings. The mechanism of the final ring‐closing event is elucidated, which reveals the counterion‐assisted nucleophilic trapping of the carbonyl moiety by the alkenyl‐gold species formed in situ. The computational evidence supports the labeling control experiments and highlights the presence of a cyclopropyl‐gold‐carbenoid intermediate in the final intramolecular 1,3‐hydrogen‐shift/skeleton‐rearrangement sequence.
Operando Attenuated Total Reflectance FTIR Spectroscopy: Studies on the Different Selectivity Observed in Benzyl Alcohol Oxidation
Authors: Villa Alberto , Ferri Davide , Campisi Sebastiano , Chan‐Thaw Carine E. , Lu Ye , Kröcher Oliver , Prati Laura 
Published: July 2015

AbstractAu, Pd, and AuPd supported on TiO2 were prepared by a sol immobilization route. Operando attenuated total reflectance (ATR) IR spectroscopy and catalytic batch reactor experiments were performed in parallel to elucidate the different catalytic performance of the catalysts in the liquid‐phase oxidation of benzyl alcohol. Pd/TiO2 exhibited a higher activity than AuPd/TiO2 and Au/TiO2, but the modification of Pd with Au demonstrated a significant stability enhancement. ATR‐IR spectroscopy evidenced that the presence of Au facilitates the desorption of byproducts, which thus reduces the extent of deactivation of the active sites caused by the irreversible adsorption of benzoate species. Although benzaldehyde was the main product in both catalysts, the nature of the byproducts differs. Pd/TiO2 favored the deoxygenation of benzyl alcohol to produce toluene as the main byproduct. Conversely, AuPd/TiO2 promoted the transformation of benzaldehyde to benzoic acid.
Grafting of Copper(I)–NHC Species on MCM‐41: Homogeneous versus Heterogeneous Catalysis
Authors: Garcés Karin , Fernández‐Alvarez Francisco J. , García‐Orduña Pilar , Lahoz Fernando J. , Pérez‐Torrente Jesús J. , Oro Luis A. 
Published: July 2015

AbstractThe copper(I) complexes [Cu(X){2,6‐diisopropylphenyl–NHC–(CH2)3Si(OiPr)3}] (X=Cl (2 a); I (2 b), NHC=N‐heterocyclic carbene) have been synthesized and characterized. Furthermore, the structure of 2 b has been confirmed by X‐ray diffraction studies. Complex 2 a has been successfully anchored in MCM‐41 to afford 2–MCM‐41. The activity of both the homogeneous, 2 a, and heterogeneous, 2–MCM‐41, catalysts in acetophenone hydrosilylation with HSiEt3 and [3+2] cycloaddition of benzyl azide and phenylacetylene has been investigated. The heterogeneous catalyst exhibits catalytic activity for the cycloaddition reaction though, unexpectedly, shows no catalytic activity for hydrosilylation.
Toluene Oxidation by Hydrogen Peroxide in Deep Eutectic Solvents
Authors: Guajardo Nadia , Carlesi Carlos , Aracena Álvaro 
Published: July 2015

AbstractThe catalytic effect of several deep eutectic solvents (DESs) on biphasic toluene oxidation by hydrogen peroxide to produce benzaldehyde was studied under various operational conditions. Experiments were performed with sodium tungstate, iron(III) chloride, phosphotungstic acid, and phosphomolybdic acid as catalysts dissolved in three DESs composed of choline chloride and a hydrogen‐bond donor molecule such as urea, glycerol, or ethylene glycol. Additionally, a fourth catalytic system composed of iron(III) chloride and choline chloride was tested. The best result was achieved with FeCl3 dissolved in the DES containing ethylene glycol, which gave 37.9 % conversion and 63.6 % selectivity. The results are better than those reported for other ionic liquids; this may be due to similar activation of hydrogen peroxide by polarization of the peroxide bond through hydrogen bonding and the low viscosity of the solvent.
Comparison of Overall Gas‐Phase Mass Transfer Coefficient for CO2 Absorption between Tertiary Amines in a Randomly Packed Column
Authors: Wen Le , Liu Helei , Rongwong Wichitpan , Liang Zhiwu , Fu Kaiyun , Idem Raphael , Tontiwachwuthikul Paitoon 
Published: July 2015

AbstractThe mass transfer performance of CO2 absorption into an innovative tertiary amine solvent, 1‐dimethylamino‐2‐propanol (1DMA2P), was investigated and compared with that of methyldiethanolamine (MDEA) in a packed column with random Dixon‐ring packing. All experiments were conducted under atmospheric pressure. The effects of inert gas flow rate, amine concentration, liquid flow rate, CO2 loading, and liquid temperature on mass transfer performance were analyzed and the results presented in terms of the volumetric overall mass transfer coefficient (KGav). The experimental findings clearly indicate that 1DMA2P provided better mass transfer performance than MDEA. For both 1DMA2P and MDEA solutions, the KGav increased with rising amine concentration and liquid flow rate, but decreased with higher CO2 loading. The inert gas flow rate only slightly affected the KGav. A satisfactory correlation of KGav was developed for the 1DMA2P‐CO2 system.
Catalyst‐Assisted Electroless Flattening of Ge Surfaces in Dissolved‐O2‐Containing Water
Authors: Kawase Tatsuya , Saito Yusuke , Mura Atsushi , Okamoto Takeshi , Kawai Kentaro , Sano Yasuhisa , Morita Mizuho , Yamauchi Kazuto , Arima Kenta 
Published: July 2015

AbstractControl of the microroughness of Ge surfaces is required to realize field‐effect transistors with high performances. We propose a novel surface‐flattening process for Ge that involves the preferential transformation of surface protrusions on Ge into soluble GeO2 with the help of a catalyst in water. To carry out this process, we developed a setup comprising a catalyst plate covered with a Pt film in contact with a Ge surface in saturated O2‐dissolved water. The role of the metallic film is to enhance the oxygen reduction reaction in water that accompanies the oxidation of protrusions or microbumps on a Ge surface. After presenting the fundamental etching properties of a Ge surface treated with this metal‐assisted chemical etching method, we demonstrate that our water‐based process creates a flattened Ge surface that has few protrusions with a lateral size on the order of 10 nm.
Radical CH Alkylation of BODIPY Dyes Using Potassium Trifluoroborates or Boronic Acids
Authors: Verbelen Bram , Cunha Dias Rezende Lucas , Boodts Stijn , Jacobs Jeroen , Van Meervelt Luc , Hofkens Johan , Dehaen Wim 
Published: July 2015

AbstractA one‐step synthetic procedure for the radical CH alkylation of BODIPY dyes has been developed. This new reaction generates alkyl radicals through the oxidation of boronic acids or potassium trifluoroborates and allows the synthesis of mono‐, di‐, tri‐, and tetraalkylated fluorophores in a good to excellent yield for a broad range of organoboron compounds. Using this protocol, multiple bulky alkyl groups can be introduced onto the BODIPY core thus creating solid‐state emissive BODIPY dyes.
Creating σ‐Holes through the Formation of Beryllium Bonds
Authors: Brea Oriana , Mó Otilia , Yáñez Manuel , Alkorta Ibon , Elguero José 
Published: July 2015

AbstractThrough the use of ab initio theoretical models based on MP2/aug‐cc‐pVDZ‐optimized geometries and CCSD(T)/aug‐cc‐pVTZ and CCSD(T)/aug‐c‐pVDZ total energies, it has been shown that the significant electron density rearrangements that follow the formation of a beryllium bond may lead to the appearance of a σ‐hole in systems that previously do not exhibit this feature, such as CH3OF, NO2F, NO3F, and other fluorine‐containing systems. The creation of the σ‐hole is another manifestation of the bond activation–reinforcement (BAR) rule. The appearance of a σ‐hole on the F atoms of CH3OF is due to the enhancement of the electronegativity of the O atom that participates in the beryllium bond. This atom recovers part of the charge transferred to Be by polarizing the valence density of the F into the bonding region. An analysis of the electron density shows that indeed this bond becomes reinforced, but the F atom becomes more electron deficient with the appearance of the σ‐hole. Importantly, similar effects are also observed even when the atom participating in the beryllium bond is not directly attached to the F atom, as in NO2F, NO3F, or NCF. Hence, whereas the isolated CH3OF, NO2F, and NO3F are unable to yield F⋅⋅⋅Base halogen bonds, their complexes with BeX2derivatives are able to yield such bonds. Significant cooperative effects between the new halogen bond and the beryllium bond reinforce the strength of both noncovalent interactions.
Dehydrogenative TEMPO‐Mediated Formation of Unstable Nitrones: Easy Access to N‐Carbamoyl Isoxazolines
Authors: Gini Andrea , Segler Marwin , Kellner Dominik , Mancheño Olga García 
Published: July 2015

AbstractN‐carbamoyl nitrones represent an important class of reagents for the synthesis of a variety of natural and biologically active compounds. These compounds are generally converted into valuable 4‐isoxazolines upon cyclization reaction with dipolarophiles. However, these types of N‐protected nitrones are highly unstable, which limits their synthesis, storage and practical use, enforcing alternative lengthy or elaborated synthetic routes. In this work, a 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO)‐mediated formal “dehydrogenation” of N‐protected benzyl‐, allyl‐ and alkyl‐substituted hydroxylamines followed by in situ trapping of the generated unstable nitrones into N‐carbamoyl 4‐isoxazolines is presented. A plausible mechanism is also proposed, in which the dipolarophile shows an important assistant role in the generation of the active nitrone intermediate. This simple protocol avoids the problematic isolation of N‐carbamoyl protected nitrones, providing new synthetic possibilities in isoxazoline chemistry.
An Indigo Carmine‐Based Hybrid Nanocomposite with Supramolecular Control of Dye Aggregation and Photobehavior
Authors: Costa Ana L. , Gomes Ana C. , Pillinger Martyn , Gonçalves Isabel S. , de Melo J. Sérgio Seixas 
Published: July 2015

AbstractZn‐Al layered double hydroxides (LDHs) containing solely indigo carmine (IC) or 1‐hexanesulfonate (HS) anions, or a mixture of the two with different HS/IC molar ratios, were prepared by the direct synthesis method and characterized by various techniques. Hydrotalcite‐type phases were obtained with basal spacings of 17.6 Å for the LDH intercalated by IC (IC‐LDH) and 18.2–18.3 Å for the other materials containing HS. From the basal spacing for IC‐LDH and UV/Vis spectroscopic data, it is proposed that the dye molecules assemble within the interlayer galleries to form a J‐type stacking arrangement. A comprehensive electronic spectral and photophysical study was undertaken for IC in solution and all materials, aiming to obtain a detailed characterization of the host–guest and guest–guest interactions. In solution (the solvent surrounded “isolated” molecule), IC presents a fast excited state proton transfer with rate constants of ∼1.2–1.4×1011 s−1, which is linked to the very efficient radiationless deactivation channel. In the solid state it is shown that incorporation of IC within the LDH decreases the level of aggregation, and that further addition of HS induces the appearance of isolated IC units within the LDH galleries. The indigo carmine‐based nanocomposites reported constitute a step forward in the design of hybrid materials with tunable properties.
A V‐Shaped Polyaromatic Amphiphile: Solubilization of Various Nanocarbons in Water and Enhanced Photostability
Authors: Kondo Kei , Akita Munetaka , Nakagawa Takafumi , Matsuo Yutaka , Yoshizawa Michito 
Published: July 2015

AbstractNanocarbons are synthetic carbon‐rich compounds with polyaromatic frameworks that have lately attracted attention as emerging functional materials. However, their extreme hydrophobicity and aggregation peculiarity, besides their shape and size diversities, precluded their study in solution, especially in “green” water. More convenient and general solubilizing methods of nanocarbon frameworks are required by using non‐covalent supramolecular interactions. Here we report a protocol for solubilizing a wide range of nanocarbons, that is, fullerenes (C60, C70, C84, and C120), polyarenes (tetracene, pentacene, perylene, coronene, and hexabenzocoronene), and carbon nanotubes (single‐walled and multi‐walled CNTs), in water through manual grinding with V‐shaped polyaromatic amphiphiles. The obtained aqueous nanocomposites are composed of nanocarbons encircled by the polyaromatic frameworks of the amphiphiles through multiple aromatic–aromatic interactions. Notably, the encapsulated photosensitive nanocarbons, such as tetracene, pentacene, and fullerene dimer, exhibit unusual stability toward UV/Vis light.
Benzo[c,d]indole‐Containing Aza‐BODIPY Dyes: Asymmetrization‐Induced Solid‐State Emission and Aggregation‐Induced Emission Enhancement as New Properties of a Well‐Known Chromophore
Authors: Shimizu Soji , Murayama Ai , Haruyama Takuya , Iino Taku , Mori Shigeki , Furuta Hiroyuki , Kobayashi Nagao 
Published: July 2015

AbstractA series of symmetric and asymmetric benzo[c,d]indole‐containing aza boron dipyrromethene (aza‐BODIPY) compounds was synthesized by a titanium tetrachloride‐mediated Schiff‐base formation reaction of commercially available benzo[c,d]indole‐2(1H)‐one and heteroaromatic amines. These aza‐BODIPY analogues show different electronic structures from those of regular aza‐BODIPYs, with hypsochromic shifts of the main absorption compared to their BODIPY counterparts. In addition to the intense fluorescence in solution, asymmetric compounds exhibited solid‐state fluorescence due to significant contribution of the vibronic bands to both absorption and fluorescence as well as reduced fluorescence quenching in the aggregates. Finally, aggregation‐induced emission enhancement, which is rare in BODIPY chromophores, was achieved by introducing a nonconjugated moiety into the core structure.
Three Series of Sulfo‐Functionalized Mixed‐Linker CAU‐10 Analogues: Sorption Properties, Proton Conductivity, and Catalytic Activity
Authors: Reimer Nele , Bueken Bart , Leubner Sebastian , Seidler Christopher , Wark Michael , De Vos Dirk , Stock Norbert 
Published: July 2015

AbstractTen mixed‐linker metal–organic frameworks [Al(OH)(m‐BDC‐X)1−y(m‐BDC‐SO3H)y] (H2BDC=1,3‐benzenedicarboxylic acid; X=H, NO2, OH) exhibiting the CAU‐10‐type structure were synthesized. The compounds can be grouped into three series according to the combination of ligands employed. The three series of compounds were obtained by employing different ratios of m‐H2BDC‐X and m‐H2BDC‐SO3Li. The resulting compounds, which are denoted CAU‐10‐H/Sx, ‐N/Sx and ‐O/Sx, show exceptionally high thermal stability for sulfonated materials of up to 350 °C. Detailed characterization with special focus on polarity and acidity was performed, and the impact of the additional SO3H groups is clearly demonstrated by changes in the sorption affinities/capacities towards several gases and water vapor. In addition, selected samples were evaluated for proton conductivity and as catalysts for the gas‐phase dehydration of ethanol to ethylene. While only very low proton conductivities were observed, a pronounced increase in catalytic activity was achieved. Although reactions were performed at temperatures of 250 and 300 °C for more than 40 h, no desulfonation and no loss of crystallinity were observed, and stable ethanol conversion resulted. This demonstrates the high stability of this material.
The Synthesis and Dynamic Structures of Multinuclear Complexes of Large Porphyrinoids Expanded by Phenylene and Thienylene Spacers
Authors: Setsune Jun‐ichiro , Toda Masayuki , Yoshida Takafumi , Imamura Keigo , Watanabe Keigo 
Published: July 2015

Abstract1,3‐Bis(2‐pyrryl)benzene was used to prepare dibenziamethyrin, in which two pyrrole units of [24]amethyrin(1.0.0.1.0.0) are replaced by benzene. 1,4‐Bis(2‐pyrryl)benzene, 2,5‐bis(2‐pyrryl)thiophene, and 4,4′‐bis(2‐pyrryl)biphenyl were also used in place of 2,2′‐bipyrrole to give expanded analogues of [24]rosarin(1.0.1.0.1.0) and [32]octaphyrin(1.0.1.0.1.0.1.0). These large porphyrinoids can incorporate multiple metal units of Rh(CO)2 and Pd(π‐allyl) with considerable deviation of the metal atoms from the dipyrrin planes, evidenced by X‐ray crystallography. The coordinated Rh(CO)2 group shuttled between both sides of the macrocycle; the rate was dependent on the spacer, ring size, and number of metal atoms. Variable temperature 1H NMR spectroscopy showed that the tris‐rhodium complexes of the expanded rosarins with 1,4‐phenylene or 2,5‐thienylene spacers adopt a C3v‐symmetric form and a Cs‐symmetric form as a result of the Rh(CO)2 groups hopping through the macrocycle cavity. The C3v‐symmetric form has a greater dipole moment and, therefore, is favored in solvents of greater polarity. The Rh(CO)2 groups in the tris‐rhodium complex of the expanded rosarin with 4,4′‐biphenylene spacers hop so fast that an averaged spectral pattern (D3h) was seen in the 1H NMR spectrum, even at −60 °C. Expanded octaphyrins with 1,4‐phenylene and 2,5‐thienylene spacers bind four Rh(CO)2 groups outside the macrocycle cavity to form a D2d‐symmetric saddle‐shaped structure that did not show any dynamic behavior on the NMR timescale, even at 80 °C. This tetranuclear complex is one of the largest porphyrinoid metal complexes characterized by X‐ray crystallography to date.
Synthesis and Thorough Investigation of Discrete Organotin Telluride Clusters
Authors: Eußner Jens P. , Kusche Ralph O. , Dehnen Stefanie 
Published: July 2015

AbstractSystematic experimental and theoretical investigations of reactions of R1SnCl3 (R1=CMe2CH2C(Me)O) with (Me3Si)2Te allowed for the stepwise formation and single‐crystalline isolation of the first tin sesquitelluride clusters with functional organic ligands. Subsequent derivatization of the latter took place under reorganization of the inorganic core, affording clusters with complex hybrid architectures.