bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dicationic μ‐Diborolyl Arene Triple‐Decker Complexes [CpCo(μ‐1,3‐C3B2Me5)M(arene)]2+ (M = Rh, Ir; Cp = Cyclopentadienyl): Synthesis, Structures, Electrochemistry and Bonding
Authors: Muratov Dmitry V. , Romanov Alexander S. , Loginov Dmitry A. , Corsini Maddalena , Fabrizi de Biani Fabrizia , Kudinov Alexander R. 
Published: January 2015

AbstractThe reaction of the bromide complexes [CpCo(μ‐1,3‐C3B2Me5)MBr2]2 [M = Rh (1), Ir (2); Cp = cyclopentadienyl] with AgBF4 in acetonitrile affords the tris(acetonitrile) μ‐diborolyl triple‐decker complexes [CpCo(μ‐1,3‐C3B2Me5)M(MeCN)3]2+ [Rh (3), Ir (4)]. The labile nitromethane solvates [CpCo(μ‐1,3‐C3B2Me5)M(MeNO2)3]2+, generated in a similar way, react with benzene and its methylated derivatives to give the arene triple‐decker complexes [CpCo(μ‐1,3‐C3B2Me5)M(arene)]2+ [M = Rh (5), Ir (6); arene = C6H6 (a), 1,2,4,5‐Me4C6H2 (b), C6Me6 (c)]. The structures of 5b(BF4)2, 5c(BF4)2, 6b(BF4)2 and 6c(BF4)2 were determined by X‐ray diffraction. The electron‐transfer ability of the arene complexes was ascertained by electrochemical techniques. In general, they are able to undergo two separate one‐electron reductions reversibly. DFT calculations revealed structural changes caused by redox processes and satisfactorily predicted the redox potentials. The second reduction is accompanied by a η6 → η4 hapticity change of the arene ligand. Energy decomposition analysis revealed that the Rh–benzene bond in cation 5a is weaker than in cyclopentadienyl analogues [(C5R5)Rh(C6H6)]2+; however, 5a proved to be the least reactive in benzene replacement with acetonitrile and mesitylene.
The Unexpected Isolation of Bismuth Tris(carboxylate) Hydrates: Syntheses and Structures of [Bi(Hsal)3(H2O)] and [Bi(Hanth)3(H2O)] (H2sal = 2‐OH‐C6H4CO2H, Hanth = 2‐NH2‐C6H4CO2H)
Authors: Kumar Ish , Andrews Phil , Whitmire Kenton H. 
Published: January 2015

AbstractA complex of the composition [Bi(2‐OH‐C6H4CO2)3(H2O)] (1) was isolated from the 1:3 reaction of BiPh3 with H2sal (H2sal = salicylic acid = 2‐OH‐C6H4CO2H) in wet xylene, and the analogous anthranilate compound [Bi(2‐NH2‐C6H4CO2)3(H2O)] (2) was obtained from the 1:3 reaction of Bi(OtBu)3 with Hanth (Hanth = anthranilic acid = 2‐NH2‐C6H4CO2H) in tetrahydrofuran. Compounds 1 and 2 were fully characterized spectroscopically and by single‐crystal X‐ray diffraction. Compounds 1 and 2 crystallize in the triclinic space group and display the η2‐(O,O′) binding mode for the oxygen atoms of the carboxylate ligands. There are two independent molecules in the asymmetric units of 1 and 2 that are connected by a weak bridging interaction of the OH or NH2 group to an adjacent molecule. Both bismuth atoms are bound to a H2O molecule, but the distances are highly asymmetric, long Bi···O lengths ranging from 2.74 to 2.89 Å.
Transition Metal Complexes with 1‐Adamantoyl Hydrazones – Cytotoxic Copper(II) Complexes of Tri‐ and Tetradentate Pyridine Chelators Containing an Adamantane Ring System
Authors: Leovac Vukadin M. , Rodić Marko V. , Jovanović Ljiljana S. , Joksović Milan D. , Stanojković Tatjana , Vujčić Miroslava , Sladić Dušan , Marković Violeta , Vojinović‐Ješić Ljiljana S. 
Published: January 2015

AbstractFive pentacoordinate copper(II) complexes with 2‐acetylpyridine or di(2‐pyridyl) ketone 1‐adamantoyl hydrazone ligands (Adpy and Addpy, respectively) of the formulae [CuCl2(Adpy)] (1), [Cu2(μ‐Cl)2(Adpy‐H)2] (2), [Cu(NCS)2(Adpy)] (3), [Cu2(μ‐Cl)2(Addpy‐H)2] (4), and [Cu2(NCS)2(μ‐Addpy‐H)2] (5) were synthesized and characterized by spectral, electrochemical, and X‐ray structural analysis. Flow cytometry and morphological analysis confirmed that the copper(II) complexes 2 and 5 induced accumulation of a sub‐G1 phase population, and fluorescence microscopy indicated the presence of large cells in apoptosis. The interaction of the copper(II) complexes with calf thymus DNA (CT‐DNA) was monitored by changes in their UV/Vis spectra. The observed intrinsic binding constants for 2 and 5 (Kb = 1.77 × 106 and 3.58 × 106 M–1, respectively) together with ethidium displacement fluorescence experiments indicate intercalative binding. Complexes 2 and 5 showed nuclease activity against pUC19 plasmid DNA.
Synthesis and Structure–Activity Relationships of Gadolinium Complexes of DO3A–Benzothiazole Conjugates as Potential Theranostic Agents
Authors: Jung Ki‐Hye , Kang Sun‐Hee , Kang Min‐Kyoung , Kim Soyeon , Kim Hee‐Kyung , Kim Yeoun‐Hee , Ho Lee Gang , Shim Gyu‐Bo , Jung Jae‐Chang , Chang Yongmin , Kim Tae‐Jeong 
Published: January 2015

AbstractThe synthesis of two bifunctional chelates, 1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid (DO3A) conjugates of benzothiazoles (H3L3a and H3L3b), and the corresponding gadolinium complexes (GdL3a and GdL3b) was achieved. The intracellular and tumor‐specific nature of GdL3a and GdL3b were confirmed by magnetic resonance images of the cytosols and nuclei of various cell lines. The two complexes displayed antitumor activities with varying degrees of growth‐inhibition and total‐growth‐inhibition values depending on the types of tumor cells. They caused morphological changes in tumor cell lines at much lower concentrations of gadolinium ([Gd] ≥ 50 μM) than their predecessors, DO3A–(p‐aniline benzothiazole) conjugates (H3L1), and its GdIII complex (GdL1) required concentrations that were almost four times as high ([Gd] ≥ 200 μM).
Drying temperature and extraction method influence physicochemical and sensory characteristics of pistachio oils
Authors: Sena‐Moreno Estela , Pardo José Emilio , Catalán Luis , Gómez Ricardo , Pardo‐Giménez Arturo , Alvarez‐Ortí Manuel 
Published: January 2015

Drying is an important operation in pistachio processing to ensure good quality. Study of drying parameters is important since they affect the quality, mainly in color, flavor and nutritional value. Hence, drying parameters could also affect pistachio oils. Pistachios of variety Larnaka were dried at different temperatures (room, 30, 50, and 70°C). Changes in physicochemical quality parameters, stability, and chemical composition of the extracted oils were evaluated. Sensory evaluation was also performed. An increase in the peroxide value was observed when pistachios were dried at 70°C or when screw press was used to extract the oil, remaining low in the rest of oils extracted with the hydraulic press. A similar pattern was observed for K270 extinction coefficient. In addition, the oils from pistachios dried at higher temperatures (50°C, 70°C) showed an increase in polyphenol content and a decrease in stigmasterol. The oxidative stability was slightly higher when screw press was used. Changes in drying temperature and extraction system had no significant effects on fatty acid composition. Color sensory tests indicated a consumer preference for oils from pistachios dried at 70°C, which produced greenish oils. Pistachio oils with different characteristics are obtained depending on the drying temperature used, both of them acceptable by consumers.Practical applicationsPistachios are considered nuts with the most nutritional value and a rich source of natural antioxidants. Drying is an important stage during pistachio processing, as it affects their oil fraction. The extraction system may also influence the characteristics of the final product. The combination of the drying temperature and extraction system may produce oils with different characteristics, which could be an interesting alternative in order to fit any consumer preferences.Physicochemical parameters and chemical composition of pistachio oils obtained by means of two pressure systems were analysed. The effect of drying temperature of the pistachios was mitigated in the oils extracted with the screw press, whereas it was clearly visible in the oils obtained with the hydraulic press. The combination of drying temperature and extraction system produces oils with different characteristics.
Linker‐Length‐Dependent Complexation of a Triptycene‐Derived Macrotricyclic Polyether with π‐Extended Viologens
Authors: Han Ying , Gu Ya‐Kun , Guo Jia‐Bin , Chen Chuan‐Feng 
Published: January 2015

AbstractComplexation between a triptycene‐derived macrotricyclic polyether and π‐extended viologens with different linker lengths in both the solution and the solid state was investigated in detail. No changes in complexation modes were observed with the host and guests of different linker length bearing methyl terminal functional groups, whereas different complexation modes were found with the host and guests of different linker length bearing methoxyethyl terminal functional groups. It was also found that two different complexation modes could exist in the same unit cell. Furthermore, we found that the binding and release of the guest in the complex could easily be controlled by addition and removal of K+ ions.
Picomolar Detection of Melamine Using Molecularly Imprinted Polymer‐Based Electrochemical Sensors Prepared by UV‐Graft Photopolymerization
Authors: Bakas Idriss , Salmi Zakaria , Jouini Mohamed , Geneste Florence , Mazerie Isabelle , Floner Didier , Carbonnier Benjamin , Yagci Yusuf , Chehimi Mohamed M. 
Published: January 2015

AbstractMolecularly imprinted polymer (MIP) films of melamine were prepared by photopolymerization of vinylic monomers on diazonium‐modified gold electrodes. The gold‐grafted MIPs are specific and selective for melamine in either organic or aqueous media. The interferent molecules cyromazine and cyanuric acid were not recognized by the MIPs. The limit of detection was as low as 1.75×10−12 mol L−1 at S/N=3. Efficiency of melamine rebinding is related to the solubility parameter of the organic solvent or pH and ionic strength of the aqueous medium. It is concluded that diazonium salts permit to design robust electrochemical MIP sensors.
A Ruthenium Based Organometallic Complex for Biosensing that is both a Stable Redox Label and a Homobifunctional Linker
Authors: Lee Yeng Ying , Parker Stephen G. , Barfidokht Abbas , Alam Muhammad Tanzirul , Walker D. Barney , Messerle Barbara A. , Gooding J. Justin 
Published: January 2015

AbstractA stable ruthenium‐based redox label, Ru(acetylacetonate)2(bipyridine‐NH2), has been synthesized with the target of circumventing the problem associated with the use of ferrocene for biosensing in solutions containing chloride ions. The redox species was shown to be highly stable with repeated cycling in biological buffers as well as being amenable to surface coupling reactions. To demonstrate the latter, the redox label was anchored onto a self‐assembled monolayer of 6‐mercaptohexanoic acid, using carbodiimide coupling, followed by binding of a pentapeptide to the redox label.
Power law statistics of cliff failures, scaling and percolation
Authors: Baldassarri Andrea , Sapoval Bernard 
Published: January 2015

AbstractLarge cliff failures have often been characterized by their size in terms of the horizontal eroded area at the cliff top, and the maximum local retreat of the coastline. Field studies suggest that the frequencies of these two quantities decrease as power laws of their respective magnitudes, defining two different decay exponents. Moreover, the horizontal area increases as a power law of the maximum local retreat, identifying a third exponent. This observation indicates that the geometry of cliff failures are similar for different magnitudes. It is shown that, under a ‘scaling hypothesis’, the exponents satisfy a precise mathematical relation that relates the exponent of the distributions of magnitudes of events and their geometry – a relation that could be useful to validate the analysis of field catalogs. In order to understand the observed scenario, a numerical model of rocky coast erosion is developed. Despite its minimal character, it reproduces the observed cliff failure statistics. Strikingly, the model precisely reproduces the geometric similarity of cliff failures observed in the field. These results suggest that the theory of percolation, which underlies the erosion model, can possibly be used as a guide to decipher the physics of rocky coast erosion and could provide precise predictions of the statistics of cliff collapses. Copyright © 2015 John Wiley & Sons, Ltd.
A compressible two‐fluid multiphase model for CO2 leakage through a wellbore
Authors: Musivand Arzanfudi Mehdi , Al‐Khoury Rafid 
Published: January 2015

SummaryThis paper introduces an effectively mesh‐independent and computationally efficient model for CO2 leakage through wellbores. A one‐dimensional compressible two‐fluid domain, representing a homogeneous air gas and a multiphase CO2 with a jump at the interface between them, is modeled.The physical domain is modeled using the drift‐flux model, and the governing equations are solved using a mixed finite‐element discretization scheme. The standard Galerkin FEM, the partition of unity method, and the level‐set method are integrated to solve the problem. All important physical phenomena and processes occurring along the wellbore path, including fluid dynamics, buoyancy, phase change, compressibility, thermal interaction, wall friction, and slip between phases, together with the jump in density and enthalpy between air and CO2, are considered. Two numerical examples illustrating the computational capability and efficiency of the model are presented. Copyright © 2015 John Wiley & Sons, Ltd.
Copper(I)‐Catalyzed Amination of Halogenopyridines with Polyamines
Authors: Anokhin Maksim V. , Averin Alexei D. , Panchenko Svetlana P. , Maloshitskaya Olga A. , Buryak Alexei K. , Beletskaya Irina P. 
Published: January 2015

AbstractCuI‐Catalyzed amination of 2‐bromo‐, and 2‐, 3‐, and 4‐iodopyridines with tri‐ and tetraamines aimed at the synthesis of N,N′‐diheteroaryl derivatives was studied. A strong dependence of the product yields on the nature of starting compounds and the ligand used was observed. The increase in the number of ethene‐1,2‐diamine fragments in the polyamine structure led to the increase in the yields of polyheteroarylated compounds, whereas propane‐1,3‐diamine fragments favored the formation of monopyridinyl derivatives and promoted the heteroarylation of the secondary amino groups. 2‐Iodopyridine, as a more reactive compound, readily formed N,N‐diarylated products. The best yields of the target N,N′‐dipyridin‐2‐yl derivatives were 76% in the case of the triamine and 68% in the case of the tetraamine. A comparison of CuI‐ and Pd0‐mediated heteroarylation of polyamines was also presented.
New Route for the Synthesis of Four‐Membered Cyclic Ketene Dithioacetals
Authors: Habibi Azizollah , Valizadeh Yousef , Alizadeh Abdolali 
Published: January 2015

AbstractNovel ketene dithioacetals have been synthesized by a one‐pot condensation reaction of active methylene compounds with CS2 in the presence of alkyl acetylenecarboxylates. This reaction proceeds in a regioselective manner and provides products in good yields. The structures of the ketene dithioacetals were characterized by IR, 1H‐ and 13C‐NMR, and MS data, and elemental analyses.
Steroidal Alkaloids from Veratrum dahuricum (Turcz.) Loes. f. with Genotoxicity on Brain Cell DNA in Mice
Authors: Cong Yue , Li Jing , Zhang Qing‐Chun , Guo Jing‐Gong , Li Sha‐Sha 
Published: January 2015

AbstractTwo new steroidal alkaloids, 2β‐hydroxyverdine (1) and tomatillidine 3‐O‐β‐D‐glucopyranoside (2), were isolated from the root and rhizome of Veratrum dahuricum (Turcz.) Loes. f., together with four known compounds, i.e., 16‐O‐(2‐methylbutyroyl)germine (3), veramitaline (4), jervine (5), and veratroylzygadenine (6). Their structures were established by extensive spectroscopic analysis, as well as by comparison with data in literature. Compounds 1–6 exhibited genotoxicity on brain cell DNA of the cerebellum and cerebral cortex in mice, evaluated by using single‐cell gel electrophoresis (comet assay).
New Flavanol Glucosides from Abacopteris aspera (Presl) Ching
Authors: Fan Zhen , Jin Jing , Lin Chaozhan , Zhu Chenchen , Yang Tao , Yang Bao , Zhu Jinping , Zhao Zhongxiang 
Published: January 2015

AbstractThree new flavanol glycosides, 1–3, and eight known compounds, 4–11, were isolated from a MeOH extract of the fern Abacopteris aspera (Presl) Ching. Their structures were elucidated on the basis of extensive spectroscopic analysis, including HSQC, HMBC, 1H,1H‐COSY, and NOESY experiments, acid hydrolysis, and by the comparison of their NMR data with those of related compounds.
Tandem Benzylic Oxidation/Dihydroxylation of α‐Vinyl‐ and α‐Alkenylbenzyl Alcohols
Authors: Fernandes Rodney A. , Kattanguru Pullaiah 
Published: January 2015

AbstractA de novo tandem benzylic oxidative dihydroxylation of α‐vinyl‐ and α‐alkenylbenzyl alcohols has been developed to give α,β‐dihydroxypropiophenones (=2,3‐dihydroxy‐1‐phenylpropan‐1‐ones) and α,β‐dihydroxyalkyl phenones. This method was shown to be substrate‐selective and specific for the oxidation of benzylic alcohols.
Absolute Configuration of Resveratrol Oligomers Isolated from Hopea utilis
Authors: Ito Tetsuro , Hoshino Ryosuke , Iinuma Munekazu 
Published: January 2015

AbstractPhytochemical studies on a stem of Hopea utilis (Dipterocarpaceae) resulted in the isolation of two new resveratrol derivatives, namely hopeaside E (1; resveratrol trimer) and hopeaside F (2; resveratrol pentamer), together with ten known resveratrol derivatives, 3–12. The structures of the new compounds were elucidated by spectroscopic analyses, including NMR experiments, and their absolute configurations were determined on the basis of a comparative configurational analysis using the β‐D‐glucopyranosyl group and chiroptical data. The absolute configuration of (+)‐balanocarpol (3) was also determined by acid‐catalyzed skeletal conversion.
Palladium‐Catalyzed Arylation of Olefins by Triarylphosphines via CP Bond Cleavage
Authors: Lu Dapeng , Xu Yu , Liu Wenjing , Guo Lijuan , Sun Xingxia 
Published: January 2015

AbstractCH Arylation of olefins by triarylphosphines via CP bond cleavage has been achieved with either Pd0 or PdII catalysts. A variety of olefins and triarylphosphines are tolerated, and we inferred that both Pd0 and PdII could function directly without pre‐oxidation or pre‐reduction.
First Stereoselective Synthesis of the Cytotoxic Polyketide (4R)‐1‐(3,5‐Dihydroxyphenyl)‐4‐hydroxypentan‐2‐one
Authors: Rajendra Prasad Kothakonda , Purushotham Reddy Sudina , Suresh Babu Katragadda , Madhusudana Rao Janaswamy 
Published: January 2015

AbstractThe first stereoselective synthesis of the cytotoxic polyketide (4R)‐1‐(3,5‐dihydroxyphenyl)‐4‐hydroxypentan‐2‐one (1) was achieved from readily available propylene oxide and 3,5‐dimethoxybenzyl alcohol. The synthesis involves Jacobsen's hydrolytic kinetic resolution (HKR) and Grignard reaction as key steps.
Synthesis of a Regioisomer of β‐Lapachone and Analogs as Potent Antitumor Agents
Authors: Ding Qunshan , Zhang Yan , Shen Zhenhua , Song Chuanjun , Chang Junbiao 
Published: January 2015

AbstractA regioisomer of β‐lapachone and two analogs were synthesized and evaluated for their antitumor activities. All three compounds tested were found to exhibit promising activities against PC‐3, HepG2, and Raji cancer cell lines in μM range.
Lithium Enolates: ‘Capricious’ Structures – Reliable Reagents for Synthesis
Authors: Braun Manfred 
Published: January 2015

AbstractThe first part of this review article deals with the structures of enolates. The development of research in this field during the last half century will be illustrated by highlightening seminal contributions, while, by no means, an attempt of comprehensiveness is made: the choice of spotlights has, admittedly, a personal touch. Aside from derivatization of lithium enolates and their crystal structures that meanwhile are classics, more recent solution studies are presented. In the second part, it will be shown by contributions of our laboratory that, despite their complicated structures, lithium enolates are reliable ‘workhorses’ in synthesis with emphasis being given to stereoselective CC bond forming reactions due to the Pd‐catalyzed allylic alkylation of non‐stabilized, preformed enolates.
Sculpting Metal‐binding Environments in De Novo Designed Three‐helix Bundles
Authors: Plegaria Jefferson S. , Pecoraro Vincent L. 
Published: January 2015

AbstractDe novo protein design is a biologically relevant approach used to study the active centers of native metalloproteins. In this review, we will first discuss the design process in achieving α3D, a de novo designed three‐helix bundle peptide with a well‐defined fold. We will then cover our recent work in functionalizing the α3D framework by incorporating a tris(cysteine) and tris(histidine) motif. Our first design contains the thiol‐rich sites found in metalloregulatory proteins that control the levels of toxic metal ions (Hg, Cd, and Pb). The latter design recapitulates the catalytic site and activity of a natural metalloenzyme carbonic anhydrase. The review will conclude with future design goals aimed at introducing an asymmetric metal‐binding site in the α3D framework.
Second Morning ACR Could Be the Alternative to First Morning ACR to Assess Albuminuria in Elderly Population
Authors: Wang Hua‐Bin , Li Rong , Liu Rui , Cui Xiao‐Fan , Pan Wen‐Jie , Sun Ao 
Published: January 2015

BackgroundAlbumin/creatinine ratio (ACR) from a first morning urine is recommended as a early indicator for diabetic nephropathy. However, it is not always feasible to collect the first morning urine for outpatients. We aimed to explore whether ACR from a second morning urine had a good consistency with that from a first morning urine to predict albuminuria in Chinese elderly citizens.MethodOne hundred and ninety‐one elderly citizens (≧60 years old) from Junliangcheng community, Dongli district, Tianjin, China were included. A first and second morning urine was collected from each participants, successfully and detected the urinary albumin and creatinine of each urine sample. Albumin to creatinine ratio from a first morning urine (ACR1) was compared with that from a second morning urine (ACR2), and the ability of ACR1 and ACR2 to predict albuminuria was assessed. Result: ACR1 and ACR2 were highly correlated (r = 0.901), especially in male and hypertension group (r = 0.938 and 0.904). The slope and intercept were 0.93 and 0.11 after log‐transformed. And there was no statistical difference between values of ACR1 and ACR2 (P = 0.271). Overall, 26.2% participants were detected with albuminuria when judged by ACR1 and 28.3% by ACR2. A good concordance of ACR category (normal or albuminuria) was found between ACR1 and ACR2 (Kappa value = 0.815 in overall; in male and hypertension group were 0.900 and 0.850).ConclusionA second morning urine ACR could be the alternative to a first morning urine ACR for albuminuria detection in elderly population.