bluuebunny/crossref_metadata_2025_split huggingface dataset:
Limitations of the Zero‐Length Column Technique to Measure Diffusional Time Constants in Microporous Adsorbents
Authors: Silva José A. C. , Rodrigues Alírio E. 
Published: October 2015

AbstractThe zero‐length column (ZLC) technique has been developed to measure the intracrystalline diffusivity of strongly adsorbed species in large zeolite crystals above 50 μm in the Henry's law range of sorption equilibrium. The ZLC is a macroscopic technique, and there is a need of large crystallites or pellets to measure the intracrystalline diffusivity Dc of fast diffusion species or the macropore diffusivity DP of weakly adsorbed species, respectively. Another limitation is that ZLC desorption curves produce similar concentration profiles (linear isotherms) in bidisperse adsorbents (pellets) under macropore or micropore diffusion control. Moreover, the forms of the response curves are very similar in both diffusion‐ and nonlinear equilibrium‐controlled processes, leading to some misinterpretations of ZLC experiments. In this work, two criteria are developed showing that, in order to macroscopically measure the micropore diffusion time constant $ r_c^2/{D_c} $
or the macropore diffusion time constant $ R_p^2(1 + K)/{D_P} $
, the time of the ZLC experiments t should be higher than 7.0 × 10−2$ r_c^2/{D_c} $
or 7.0 × 10−2$ R_p^2(1 + K)/{D_P} $
, respectively. The interpretation of the ZLC response curve data is also checked in two completely different regimes, showing that a single ZLC response curve is not enough to conclude if a system is under a kinetic or an equilibrium regime.
Electrical Conductivity and Strong Luminescence in Copper Iodide Double Chains with Isonicotinato Derivatives
Authors: Hassanein Khaled , Conesa‐Egea Javier , Delgado Salome , Castillo Oscar , Benmansour Samia , Martínez José I. , Abellán Gonzalo , Gómez‐García Carlos J. , Zamora Félix , Amo‐Ochoa Pilar 
Published: October 2015

AbstractDirect reactions between CuI and isonicotinic acid (HIN) or the corresponding esters, ethyl isonicotinate (EtIN) or methyl isonicotinate (MeIN), give rise to the formation of the coordination polymers [CuI(L)]n with L=EtIN (1), MeIN (2) and HIN (3). Polymers 1–3 show similar structures based on a CuI double chain in which ethyl‐, methyl isonicotinate or isonicotinic acid are coordinated as terminal ligands. Albeit, their supramolecular architecture differs considerably, affecting the distances and angles of the central CuI double chains and thereby their physical properties. Hence, the photoluminescence shows remarkable differences; 1 and 2 show a strong yellow emission, whereas 3 displays a weak emission; and 1 and 2 are semiconductors with moderate room temperature conductivities, whereas 3 has increased electrical conductivity up to 3×10−3 S cm−1. Additionally, 1 and 2 present an irreversible transition to a highly conducting phase with a conductivity almost 4 orders of magnitude higher and a quasi‐metallic behaviour. Thermogravimetric analysis (TGA) coupled to a mass spectrometer and magnetic measurements point to a partial thermally induced oxidation of the carboxylate groups of the ligands with CuI to Cu0 reduction. DFT calculations have been carried out to rationalise these observations.
Preparation, Structural Determination, and Characterization of Electronic Properties of Bis‐silylated and Bis‐germylated Lu3N@Ih‐C80
Authors: Kako Masahiro , Miyabe Kyosuke , Sato Kumiko , Suzuki Mitsuaki , Mizorogi Naomi , Wang Wei‐Wei , Yamada Michio , Maeda Yutaka , Olmstead Marilyn M. , Balch Alan L. , Nagase Shigeru , Akasaka Takeshi 
Published: October 2015

AbstractBis‐silylated and bis‐germylated derivatives of Lu3N@Ih‐C80 (3, 4, 5) were successfully synthesized by the photochemical addition of disiliranes 1 a, 1 b or digermirane 2, and fully characterized by spectroscopic, electrochemical, and theoretical studies. Interestingly, digermirane 2 reacts more efficiently than disiliranes 1 a and 1 b because of its good electron‐donor properties and lower steric hindrance around the GeGe bond. The 1,4‐adduct structures of 3, 4, 5 were unequivocally established by single‐crystal X‐ray crystallographic analyses. The electrochemical and theoretical studies reveal that the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the 1,4‐adducts are remarkably smaller than those of Lu3N@Ih‐C80, because the electron‐donating groups effectively raise the HOMO levels. It is also observed that germyl groups are slightly more electron‐donating than the silyl groups on the basis of the redox properties and the HOMO–LUMO energies of 4 and 5. Bis‐silylation and bis‐germylation are effective and versatile methods for tuning the electronic characteristics of endohedral metallofullerenes.
Exploratory Study on the RNA‐Binding Structural Motifs by Library Screening Targeting pre‐miRNA‐29 a
Authors: Fukuzumi Takeo , Murata Asako , Aikawa Haruo , Harada Yasue , Nakatani Kazuhiko 
Published: October 2015

AbstractThe metabolic stream of microRNA (miRNA) production, the so‐called maturation process of miRNAs, became one of important metabolic paths for drug‐targeting to modulate the expression of genes related to a number of diseases. We carried out discovery studies on small molecules binding to the precursor of miR‐29a (pre‐miR‐29a) from a chemical library containing 41 119 compounds (AQ library) by the fluorescent indicator displacement (FID) assay using the xanthone derivative X2SdiMe as a fluorescent indicator. The FID assay provided 1075 compounds, which showed an increase of fluorescence. These compounds were subsequently submitted to a binding analysis in a surface plasmon resonance (SPR) assay on a pre‐miR‐29a immobilized surface. 21 hit compounds were identified with a good reproducibility in the binding. These compounds have not been reported to bind to RNA until now and can be classified into two groups on the basis of the kinetics in the binding. To gain more information on the motif structures that could be necessary for the binding to pre‐miR‐29a, 19 substructures were selected from the hit compounds. The substructure library (SS library) which consisted of 362 compounds was prepared from the AQ library. An SPR assay of the SS library on pre‐miR‐29a‐immobilized surface suggested that five substructures could potentially be important structural motifs to bind to pre‐miR‐29a. These studies demonstrate that the combination of FID‐based screening of chemical library and subsequent SPR assay would be one way for obtaining practical solutions for the discovery of molecules which bind to the target pre‐miRNAs.
Catalytic Asymmetric Michael Reaction of 5H‐Oxazol‐4‐Ones with α,β‐Unsaturated Acyl Imidazoles
Authors: Zhang Bangzhi , Han Fengxia , Wang Linqing , Li Dan , Yang Dongxu , Yang Xiaoli , Yang Junxian , Li Xiaofang , Zhao Depeng , Wang Rui 
Published: October 2015

AbstractThe asymmetric Michael reaction between 5H‐oxazol‐4‐ones and α,β‐unsaturated acyl imidazoles is reported. A novel 2‐benzo[b]thiophenyl‐modified chiral ProPhenol species is synthesized and used as a ligand, leading to good enantioselectivities in this asymmetric conjugate addition reaction. Furthermore, the introduction of phenol additives as achiral co‐ligands is found to improve the reaction’s chemical yields, diastereoselectivities, and enantioselectivities.
To Transfer or Not to Transfer? Development of a Dinitrosyl Iron Complex as a Nitroxyl Donor for the Nitroxylation of an FeIII–Porphyrin Center
Authors: Tseng Yu‐Ting , Chen Chien‐Hong , Lin Jing‐Yu , Li Bing‐Han , Lu Yu‐Huan , Lin Chia‐Her , Chen Hsin‐Tsung , Weng Tsu‐Chien , Sokaras Dimosthenes , Chen Huang‐Yeh , Soo Yun‐Liang , Lu Tsai‐Te 
Published: October 2015

AbstractA positive myocardial inotropic effect achieved using HNO/NO−, compared with NO⋅, triggered attempts to explore novel nitroxyl donors for use in clinical applications in vascular and myocardial pharmacology. To develop M‐NO complexes for nitroxyl chemistry and biology, modulation of direct nitroxyl‐transfer reactivity of dinitrosyl iron complexes (DNICs) is investigated in this study using a FeIII‐porphyrin complex and proteins as a specific probe. Stable dinuclear {Fe(NO)2}9 DNIC [Fe(μ‐MePyr)(NO)2]2 was discovered as a potent nitroxyl donor for nitroxylation of FeIII‐heme centers through an associative mechanism. Beyond the efficient nitroxyl transfer, transformation of DNICs into a chemical biology probe for nitroxyl and for pharmaceutical applications demands further efforts using in vitro/in vivo studies.
Instantaneous Click Chemistry by a Copper‐Containing Polymeric‐Membrane‐Installed Microflow Catalytic Reactor
Authors: Yamada Yoichi M. A. , Ohno Aya , Sato Takuma , Uozumi Yasuhiro 
Published: October 2015

AbstractThe copper(I)‐catalyzed Huisgen cycloaddition (azide–alkyne cycloaddition) is an important reaction in click chemistry that ideally proceeds instantaneously. An instantaneous Huisgen cycloaddition has been developed that uses a novel catalytic dinuclear copper complex‐containing polymeric membrane‐installed microflow device. A polymeric membranous copper catalyst was prepared from poly(4‐vinylpyridine), copper(II) sulfate, sodium chloride, and sodium ascorbate at the interface of two laminar flows inside microchannels. Elucidation of the structure by XANES, EXAFS, and elemental analysis, as well as second‐order Møller–Plesset perturbation theory (MP2) calculations and density functional theory (DFT) calculations assigned the local structure near Cu as a μ‐chloro dinuclear CuI complex. The microflow device promotes the instantaneous click reaction of a variety of alkynes and organic azides to afford the corresponding triazoles in quantitative yield.
Through‐Space 1,4‐Palladium Migration and 1,2‐Aryl Shift: Direct Access to Dibenzo[a,c]carbazoles through a Triple CH Functionalization Cascade
Authors: Bhunia Samir Kumar , Polley Arghya , Natarajan Ramalingam , Jana Ranjan 
Published: October 2015

AbstractA palladium‐catalyzed expeditious synthesis of dibenzofused carbazoles from readily available 2‐arylindoles and diaryliodonium salts is reported. Interestingly, after the electrophilic C3 palladation of indole, an unexpected “through‐space” 1,4‐palladium migration to the 2‐aryl moiety, by remote CH bond activation followed by CH arylation with diaryliodonium salt, and an unprecedented 1,2‐aryl shift take place. Finally, an intramolecular cross‐dehydrogenative coupling (CDC) at the C2 position affords dibenzo[a,c]carbazoles in high yields. Remarkably, the present migratory annulation occurs through three CH bond activation one CC bond cleavage, and the simultaneous construction of three new CC bonds in a single operation.
Nonstoichiometric, Protic Azolium Azolate Ionic Liquids Provide Unique Environments for N‐Donor Coordination Chemistry
Authors: Kelley Steven P. , Nuss Joseph S. , Rogers Robin D. 
Published: October 2015

AbstractHere we demonstrate that neat reactions of amphoteric azoles with more basic azoles give a family of finely tunable, nonstoichiometric liquids which are useful for N‐donor coordination chemistry. Reacting 4,5‐dicyanoimidazole (4,5‐DCNIm) with 1‐methylimidazole (1‐mim) gives new compounds with composition‐dependent speciation. Two crystalline compounds, a 1:1 protic salt, [H(1‐mim)][4,5‐DCNIm], and a 1:2 salt co‐crystal, [H(1‐mim)][4,5‐DCNIm]⋅4,5‐DCNIm, were isolated and structurally characterized, while differential scanning calorimetry revealed both suppression of crystallization and the presence of neutral and anionic species in the melt. Reactions of Cu(NO3)2⋅2.5 H2O, CuO, and ZnO with the neat 2:1 1‐mim/4,5‐DCNIm melt resulted in the isolation of entirely N‐donor ligated complexes of the formula M(4,5‐DCNIm)2(1‐mim)4 (M=Cu, Zn).
Direct Catalytic Asymmetric Mannich‐Type Reaction of α‐N3 Amide
Authors: Sun Zhongdong , Weidner Karin , Kumagai Naoya , Shibasaki Masakatsu 
Published: October 2015

AbstractAn α‐N3 7‐azaindoline amide serves as a latent enolate to directly engage in an asymmetric Mannich‐type reaction with N‐thiophosphinoyl imines by the action of a cooperative catalyst. The thus‐obtained highly enantioenriched anti‐adduct was transformed into β‐amino‐α‐azido acid in high yield by simple acidic treatment.
Chiral Pool‐Based Synthesis of Naphtho‐Fused Isocoumarins
Authors: Raza Abdul Rauf , Saddiqa Aisha , Çakmak Osman 
Published: October 2015

AbstractA variety of chiral derivatives of benzo[d]naphtho[1,2‐b]pyran‐6‐one were prepared in a single step by Et3N‐mediated condensation of homophthalic anhydride with different derivatives of (S)‐amino acid chlorides at –5 °C by employing a chiral pool methodology. Chirality 27:951–957, 2015. © 2015 Wiley Periodicals, Inc.
Synthesis and properties of polyethylene/TiO2 nanocomposites using a vanadium catalyst
Authors: Bakather Omer Yahya , Al‐harthi Mamdouh A. 
Published: October 2015

AbstractIn this study, a vanadium (III) complex bearing a salicylaldiminato ligand of the general formula [RN=CH(2,4‐tBu2C6H2O)]VCl2(THF)2, where R = 2,6‐iPr2C6H3, was used as a catalyst. Titanium dioxide doped with iron nanofillers was synthesized by a sol‐gel process and used to investigate the effect of nanofillers on ethylene homopolymer and ethylene/propylene copolymer properties. To the best of our knowledge, this is the first time titanium dioxide doped with iron has been used as a nanofiller in ethylene polymerization and ethylene/propylene copolymerization using a vanadium complex with methyl aluminum dichloride as a cocatalyst. Besides catalyst activity, the molecular mass (Mw) of the obtained polymer, molecular mass distribution, copolymer composition, crystallinity, and thermal characteristics of polyethylene and polyethylene/polypropylene nanocomposites were investigated.
Mesozoic and Cenozoic Tectono‐Thermal Evolution History in the Chagan sag, Inner Mongolia
Authors: Yin‐Hui ZUO , Wang ZHANG , Zhao‐Ying LI , Jia‐Wei LI , Qing‐Qing HAO , Jie HU 
Published: October 2015

AbstractThe Chagan sag has the greatest oil and gas exploration potential among other sags in the Yingen‐Ejinaqi Basin, Inner Mongolia. To reveal the tectono‐thermal evolution history of the Chagan sag, this article utilized the combined forward and inversion method and 35 apatite fission track and 119 vitrinite reflectance data to reconstruct the Mesozoic and Cenozoic tectono‐thermal evolution history in the Chagan sag. The results show that the Chagan sag had a high geothermal gradient during the Cretaceous, and it experienced the following 4 stages of tectono‐thermal evolutions: (1) a rapid geothermal gradient increase stage from the Bayingebi Formation depositional period to the Suhongtu Formation depositional period, during which the geothermal gradient increased to 46∼52 °C/km at the end of the Suhongtu Formation depositional period; (2) a geothermal gradient peak stage during the Yingen Formation depositional period, with maximum geothermal gradient ranged from 50 to 58 °C/km; (3) a high geothermal gradient continuation stage during the Wulansuhai Formation depositional period, with maximum geothermal gradient ranged from 39 to 48 °C/km; and (4) a thermal subsidence stage during the Cenozoic, during which the Chagan sag is in the uplift and erosion stage due to the Himalayan movement and the geothermal gradient gradually decreased to 31∼34 °C/km at the present day. Moreover, the tectono‐thermal evolution was consistent with the tectonic evolution and volcanic activities in the Chagan sag. During the Early Cretaceous, the intraplate rift was developed, lithosphere was thinned and multi‐phase intense volcanic rocks were erupted in the Chagan sag, so a large amount of energy was released to the surface from the deep crust, resulting in a high geothermal gradient during this period. In addition, the high geothermal gradient during the Cretaceous was favorable for hydrocarbon generation, corresponding to a shallow paleo‐generation threshold, and the Early Cretaceous geothermal fields controlled the hydrocarbon generation of the Chagan sag. This work may provide new insights for the understanding of the oil and gas exploration potential of the Chagan sag.
The Relationship between High Conductive Layer in Upper Mantle and Endogenous Metallic Ore and Petroleum Reservoir
Authors: Qing ZHONG , Hui FANG , Pi‐Yuan YANG , Li LI , Yong‐Zhen YUAN , Fa‐Gen PEI 
Published: October 2015

AbstractBased on the 1° × 1° depth map of the high conductive layers in upper mantle of China (1996), with the addition of magnetotelluric data, we created the new map of the high conductive layer in upper mantle of China. The depth of the upper mantle high conductive layers vary widely in China, the shallowest depth is about 50∼60 km, the deepest place is about 230 km, and the average depth can be about 100∼120 km. Through further study on the interface depth of high conductive layer in upper mantle as well as contrasting with the distribution of endogenous metallic minerals of the continent of China, we have found that most of the endogenous metallic ore deposits are located at the top of high conductive layer in upper mantle uplift or the top of the steep gradient zone of high conductive layer in upper mantle. Therefore, the depth and shape of the high‐conductive layer in upper mantle can be very useful for the prediction of endogenous metal ores. We also found that the structures which have mirror relationship with the high conductive layer in upper mantle such as shallow basin and rift are the best area to detecting inorganic mantle reservoirs. The lithosphere are thinning and stretching while the uplift of high conductive layer in upper mantle, meanwhile a series of nearly parallel beam steep crack can be formed to become the passway for the mass upwelling of magma, liquid and gas from the deep mantle, finally all those materials from deep mantle are accumulated and become inorganic mantle reservoirs, gas reservoirs and endogenous metal ores under certain situations.
Increased risk of second malignant neoplasms in adolescents and young adults with cancer
Authors: Lee Jean S. , DuBois Steven G. , Coccia Peter F. , Bleyer Archie , Olin Rebecca L. , Goldsby Robert E. 
Published: October 2015

BACKGROUNDThe authors describe the incidence and characteristics of secondary malignant neoplasms (SMNs) in adolescent and young adult (AYA) cancer survivors compared with those in younger and older cancer survivors.METHODSChildren aged ≤14 years, AYAs aged 15 to 39, and older adults aged ≥40 years at the time of primary diagnosis who were reported as cancer survivors in the Surveillance, Epidemiology, and End Results (SEER) program between 1973 and 2011 were compared in this population‐based analysis. The primary analysis was the risk that an SMN would occur ≥5 years after the original diagnosis for patients who had the more common AYA cancers (leukemia, lymphoma, testicular malignancy, ovarian malignancy, melanoma, and cancers of the thyroid, breast, soft tissue, or bone). The standardized incidence ratio (SIR), absolute excess risk (AER), and cumulative incidence of SMN for the selected cancers were assessed. The risk of SMN for the entire cohort also was analyzed.RESULTSOf the 148,558 AYA survivors who were diagnosed with a selected cancer, 7384 developed an SMN 5 years after their original diagnosis. The SIRs (95% confidence intervals [CIs]) were 1.58 (95% CI, 1.55‐1.62) for AYAs, 4.26 (95% CI, 3.77‐4.80) for children, and 1.10 (95% CI, 1.09‐1.11) for older adults, and the AERs were 22.9, 16.6, and 14.7, respectively. The cumulative incidence of SMN at 30 years was 13.9% for the AYA group. The most common SMNs in AYAs were breast cancer, gastrointestinal cancer, genital cancers, and melanoma. AYAs who had received radiation therapy had a higher cumulative incidence of SMN.CONCLUSIONSAYAs who survive cancer for more than 5 years have a higher relative risk of SMN compared with the general population and have a higher absolute risk of SMN compared with younger or older cancer survivors. Cancer 2016;122:116–123. © 2015 American Cancer Society.
BRCA1 and BRCA2 mutations in Japanese patients with ovarian, fallopian tube, and primary peritoneal cancer
Authors: Sakamoto Ikuko , Hirotsu Yosuke , Nakagomi Hiroshi , Ouchi Hidetaka , Ikegami Atsushi , Teramoto Katsuhiro , Amemiya Kenji , Mochizuki Hitoshi , Omata Masao 
Published: October 2015

BACKGROUNDThe contribution of BRCA1 and BRCA2 to ovarian cancer in Japanese patients is still unclear. This study investigated the frequency of germline mutations in BRCA1/2 in Japanese patients with ovarian, peritoneal, or fallopian tube cancer, regardless of their family histories, which were suggestive of hereditary breast and ovarian cancer.METHODSNinety‐five unselected women with ovarian cancer who were seen from 2013 to 2015 at Yamanashi Prefectural Central Hospital were enrolled. Analyses of BRCA1/2 gene mutations were performed with next‐generation sequencing.RESULTSTwelve of the 95 patients (12.6%), including 5 in the BRCA1 (5.3%) and 7 in the BRCA2 (7.4%), had deleterious mutations. Among the 36 cases with a family history, 6 (16.7%) were found to carry mutations in BRCA1 and BRCA2. Notably, 6 of the 59 cases (10.2%) without a family history also had BRCA1/2 germline mutations. There was no statistical difference between the 2 groups (P = .36). The presence of mutations and their clinical relevance were studied. Mutation carriers were diagnosed at advanced stages (100% of positive cases among stage III or IV cases) and had poor prognostic histological subtypes (100% of positive cases had high‐grade serous adenocarcinomas).CONCLUSIONSIn this unselected Japanese population, approximately 13% of the cases with ovarian cancer appeared to be associated with an inherited risk, regardless of a family history. This finding indicates that BRCA1/2 genetic testing should be performed for all patients with ovarian cancers. Cancer 2016;122:84–90. © 2015 American Cancer Society.