bluuebunny/crossref_metadata_2025 huggingface dataset:
Investigation of nanostructured TiO2 surface and interface electric fields with photoreflectance spectroscopy
Authors: Sellers Meredith C. K. , Seebauer Edmund G.
Published: August 2012

The electrical properties of buried solid–solid interfaces are essential to the optimization of devices such as dye‐sensitized solar cells and photocatalysts. The degree of fixed charge buildup at these interfaces can be sample‐dependent, influenced by only a small fraction of total surface sites, and challenging to quantify. This work describes the applicability of photoreflectance spectroscopy (PR) to the characterization of thin film nanostructured TiO2. The approach involves the synthesis of polycrystalline anatase TiO2 on quartz and Si(100) by atomic layer deposition with Ti(OCH(CH3)2)4 and H2O as precursors. PR reveals negligible band bending at the TiO2 free surface. A distinct spectral feature at 299.0 ± 0.3 kJ/mol (3.10 ± 0.0031 eV) is attributed to electronic states at the TiO2‐Si interface. Temporal variations in the magnitude of this feature are discussed in the context of bulk carrier concentration, solid–solid interface chemical reactions, and charge exchange between interface and grain boundary states and the bulk bands. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1049–1055, 2013
Reduction of a single granule drying model: An essential step in preparation of a population balance model with a continuous growth term
Authors: Mortier Séverine Thérèse F.C. , Van Daele Timothy , Gernaey Krist V. , De Beer Thomas , Nopens Ingmar
Published: August 2012

The development of a Population Balance Model (PBM) for a pharmaceutical granule drying process requires a continuous growth term; the latter actually represents the drying process as the moisture content is the internal coordinate of the PBM. To establish such a PBM, a complex drying model for a single granule needs reduction in complexity. The starting point is a detailed model that describes the drying behavior of single pharmaceutical granules. A Global Sensitivity Analysis (GSA) was performed to detect the most sensitive degrees of freedom in the model as these need to be retained in the reduced model. Simulations of the complex drying model were, in a next phase, used to develop the reduced model, which describes the decrease of the moisture content in function of the gas temperature. The developed reduced model was then included in a Population Balance Equation (PBE) to describe the drying behavior of a population of granules. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1127–1138, 2013
Reversal Effect of Melanoma Differentiation Associated Gene‐7/Interleukin‐24 on Multidrug Resistance in Human Hepatocellular Carcinoma Cells
Authors: Fang Ping , Zhang Xin , Gao Yan , Ding Chang‐Rui , Cui Fang , Jiao Shun‐Chang
Published: August 2012

Multidrug resistance is the main cause for failure of chemotherapy. Melanoma differentiation associated gene‐7/interleukin‐24 (mda‐7/IL‐24) has been implicated in the inhibition of human tumor cell proliferation. However, the reversing effect of mda‐7/IL‐24 on multidrug resistance of human hepatocellular carcinoma (HCC) is not fully clear. In this study, we investigated the effects of overexpression of the mda‐7/IL‐24 gene in human HCC. We established mda‐7/IL‐24 overexpressing BEL‐7402/5‐fluorouracil (5‐FU) cell lines and their drug sensitivity to 5‐FU and doxorubicin (DOX) which were investigated by MTT. Furthermore, we investigated the apoptotic rate and the intracellular accumulation of Rhodamine‐123 and DOX by flow cytometry. We also studied the expression of multidrug resistance gene 1 (MDR1), lung resistance‐related protein (LRP), and multidrug resistance‐related protein 1 (MRP1) by real‐time polymerase chain reaction and Western blotting. Transcriptional activation of AP‐1 and NF‐κB was determined by luciferase reporter assay. The drug sensitivity of 5‐FU or DOX, the apoptotic rate, and the intracellular accumulation of Rhodamine‐123 and DOX were increased, while the mRNA and protein expression levels of MDR1, LRP, and MRP1 were reduced. The transcriptional activation of AP‐1 and NF‐κB was suppressed in mda‐7/IL‐24 overexpressing BEL‐7402/5‐FU cells. Our results demonstrated that mda‐7/IL‐24 could restore the drug sensitivity through the downregulation of MDR1, MRP1, and LRP expression, as well as the transcriptional activation of AP‐1 and NF‐κB and effectively reverse MDR. Anat Rec, 2012. © 2012 Wiley Periodicals, Inc.
Quantum dot binding to DNA: Single‐molecule imaging with atomic force microscopy
Authors: Li Kungang , Zhang Wen , Chen Yongsheng
Published: August 2012

The interaction between nanoparticles (NPs) and DNA is of significance for both application and implication research of NPs. In this study, a single‐molecule imaging technique based on atomic force microscopy (AFM) was employed to probe the NP‐DNA interactions with quantum dots (QDs) as model NPs. Reproducible high‐quality images of single DNA molecules in air and in liquids were acquired on mica by optimizing sample preparation conditions. Furthermore, the binding of QDs to DNA was explored using AFM. The DNA concentration was found to be a key factor influencing AFM imaging quality. In air and liquids, the optimal DNA concentration for imaging DNA molecules was approximately 2.5 and 0.25 μg/mL, and that for imaging DNA binding with QDs was 0.5 and 0.25 μg/mL, respectively. In the presence of QDs, the DNA conformation was altered with the formation of DNA condensates. Finally, the fine conformation of QD‐DNA binding sites was examined to analyze the binding mechanisms. This work will benefit investigations of NP‐DNA interactions and the understanding of the structure of NP‐DNA bioconjugates.

See accompanying article by Wang DOI: 10.1002/biot.201200309
Molecular crosstalk between cancer cells and tumor microenvironment components suggests potential targets for new therapeutic approaches in mobile tongue cancer
Authors: Dayan Dan , Salo Tuula , Salo Sirpa , Nyberg Pia , Nurmenniemi Sini , Costea Daniela Elena , Vered Marilena
Published: August 2012

We characterized tumor microenvironment (TME) components of mobile tongue (MT) cancer patients in terms of overall inflammatory infiltrate, focusing on the protumorigenic/anti‐inflammatory phenotypes and on cancer‐associated fibroblasts (CAFs) in order to determine their interrelations and associations with clinical outcomes. In addition, by culturing tongue carcinoma cells (HSC‐3) on a three‐dimensional myoma organotypic model that mimics TME, we attempted to investigate the possible existence of a molecular crosstalk between cancer cells and TME components. Analysis of 64 cases of MT cancer patients revealed that the overall density of the inflammatory infiltrate was inversely correlated to the density of CAFs (P = 0.01), but that the cumulative density of the protumorigenic/anti‐inflammatory phenotypes, including regulatory T cells (Tregs, Foxp3+), tumor‐associated macrophages (TAM2, CD163+), and potentially Tregs‐inducing immune cells (CD80+), was directly correlated with the density of CAFs (P = 0.01). The hazard ratio (HR) for recurrence in a TME rich in CD163+ Foxp3+ CD80+ was 2.9 (95% CI 1.03–8.6, P = 0.043 compared with low in CD163+ Foxp3+ CD80+). The HR for recurrence in a TME rich in CAFs was 4.1 (95% confidence interval [CI] 1.3–12.8, P = 0.012 compared with low in CAFs). In vitro studies showed cancer‐derived exosomes, epithelial–mesenchymal transition process, fibroblast‐to‐CAF‐like cell transdifferentiation, and reciprocal interrelations between different cytokines suggesting the presence of molecular crosstalk between cancer cells and TME components. Collectively, these results highlighted the emerging need of new therapies targeting this crosstalk between the cancer cells and TME components in MT cancer.
Chemical Shifts in Nucleic Acids Studied by Density Functional Theory Calculations and Comparison with Experiment
Authors: Fonville Judith M. , Swart Marcel , Vokáčová Zuzana , Sychrovský Vladimír , Šponer Judit E. , Šponer Jiří , Hilbers Cornelis W. , Bickelhaupt F. Matthias , Wijmenga Sybren S.
Published: August 2012

NMR chemical shifts are highly sensitive probes of local molecular conformation and environment and form an important source of structural information. In this study, the relationship between the NMR chemical shifts of nucleic acids and the glycosidic torsion angle,χ, has been investigated for the two commonly occurring sugar conformations. We have calculated by means of DFT the chemical shifts of all atoms in the eight DNA and RNA mono‐nucleosides as a function of these two variables. From the DFT calculations, structures and potential energy surfaces were determined by using constrained geometry optimizations at the BP86/TZ2P level of theory. The NMR parameters were subsequently calculated by single‐point calculations at the SAOP/TZ2P level of theory. Comparison of the1H and13C NMR shifts calculated for the mono‐nucleosides with the shifts determined by NMR spectroscopy for nucleic acids demonstrates that the theoretical shifts are valuable for the characterization of nucleic acid conformation. For example, a clear distinction can be made betweenχangles in theantiandsyndomains. Furthermore, a quantitative determination of theχangle in thesyndomain is possible, in particular when13C and1H chemical shift data are combined. The approximate linear dependence of the C1′ shift on theχangle in theantidomain provides a good estimate of the angle in this region. It is also possible to derive the sugar conformation from the chemical shift information. The DFT calculations reported herein were performed on mono‐nucleosides, but examples are also provided to estimate intramolecularly induced shifts as a result of hydrogen bonding, polarization effects, or ring‐current effects.
Visible‐Light‐Induced Photocatalytic Hydrogen Production over Binuclear RuII–Bipyridyl Dye‐Sensitized TiO2 without Noble Metal Loading
Authors: Zhang Xiaohu , Veikko Uahengo , Mao Jin , Cai Ping , Peng Tianyou
Published: August 2012

Highly efficient, visible light induced photocatalytic H2 production was achieved over a TiO2 system sensitized by binuclear RuII bipyridyl (bpy) complex [Ru2(bpy)4(BL)](ClO4)2 (BL=bridging ligand) without Pt loading, which is almost unaffected by pH in aqueous solution in the wide range from pH 5.00 to 10.50, although the dye molecules can only be loosely attached to TiO2 due to the absence of terminal carboxyl groups. The photocatalyst shows remarkable long‐term stability and reproducibility of H2 evolution even after exchanging the aqueous triethanolamine solution. The amount of H2 evolved over 100 mg of photocatalyst in 27 h of irradiation corresponds to a turnover number of about 75 340, and the apparent quantum yields are estimated to be 16.8 and 7.3 % under 420 and 475 nm monochromatic light irradiation, respectively. A comparative study shows that the loosely attached dye [Ru2(bpy)4(BL)](ClO4)2 has higher photosensitization efficiency than tightly linked dyes with terminal carboxyl groups, such as [Ru2(dcbpy)4(BL)](ClO4)2 and N719. It can be rationalized by their different coordination, physicochemical, electron‐injection, and back‐transfer properties.
Acceptor‐Substituted Ferrocenium Salts as Strong, Single‐Electron Oxidants: Synthesis, Electrochemistry, Theoretical Investigations, and Initial Synthetic Application
Authors: Khobragade Dushant A. , Mahamulkar Shraddha G. , Pospíšil Lubomír , Císařová Ivana , Rulíšek Lubomír , Jahn Ullrich
Published: August 2012

A series of mono‐ and 1,1′‐diheteroatom‐substituted ferrocene derivatives as well as acylated ferrocenes was prepared efficiently by a unified strategy that consists of selective mono‐ and 1,1′‐dilithiation reactions and subsequent coupling with carbon, phosphorus, sulfur and halogen electrophiles. Chemical oxidation of the ferrocene derivatives by benzoquinone, 2,3‐dichloro‐5,6‐dicyanobenzoquinone, AgPF6, or 2,2,6,6‐tetramethyl‐1‐oxopiperidinium hexafluorophosphate provided the corresponding ferrocenium salts. The redox potentials of the synthesized ferrocenes were determined by cyclic voltammetry, and it was observed that all new ferrocenium salts have stronger oxidizing properties than standard ferrocenium hexafluorophosphate. An initial application of selected derivatives in an oxidative bicyclization revealed that they mediate the transformation under considerably milder conditions than ferrocenium hexafluorophosphate. Quantum chemical calculations of the reduction potentials of the substituted ferrocenium ions were carried out by using a standard thermodynamic cycle that involved the gas‐phase energetics and solvation energies of the contributing species. A remarkable agreement between theory and experiment was found: the mean average deviation amounted to only 0.030 V and the maximum deviation to 0.1 V. This enabled the analysis of various physical contributions to the computed reduction potentials of these ferrocene derivatives, thereby providing insight into their electronic structure and physicochemical properties.
Self‐Assembled Pd6 Open Cage with Triimidazole Walls and the Use of Its Confined Nanospace for Catalytic Knoevenagel‐ and Diels–Alder Reactions in Aqueous Medium
Authors: Samanta Dipak , Mukherjee Sandip , Patil Yogesh P. , Mukherjee Partha Sarathi
Published: August 2012

The two‐component self‐assembly of a 90° PdII acceptor and a triimidazole donor led to the formation of a water‐soluble semi‐cylindrical cage with a hydrophobic cavity, which was separately crystallized with hydrophilic‐ and hydrophobic guests. The parent cage was found to catalyze the Knoevenagel condensation reaction of a series of aromatic mono‐aldehydes with active methylene compounds, such as Meldrum′s acid or 1,3‐dimethylbarbituric acid. The confined hydrophobic nanospace within this cage was also used in the catalytic Diels–Alder reactions of 9‐hydroxymethylanthracene with N‐phenylmaleimide or N‐cyclohexylmaleimide.
ChemInform Abstract: Infrared Spectroscopic and Theoretical Investigations of the OUF2 and OThF2 Molecules with Triple Oxo Bond Character.
Authors: Gong Yu , Wang Xuefeng , Andrews Lester , Schloeder Tobias , Riedel Sebastian
Published: August 2012

The title molecules are prepared by reaction of OF2 molecules with laser ablated uranium and thorium atoms in solid argon and neon.
ChemInform Abstract: Optical and Structural Properties of Ni2+‐Doped Magnesium Gallate Polycrystalline Samples.
Authors: Costa G. K. B. , Sosman L. P. , Lopez A. , Cella N. , Barthem R. B.
Published: August 2012

Mg1‐xNixGa2O4 (x = 0.001, 0.005, 0.01) is synthesized by solid state reaction of MgO, Ga2O3, and Ni(OH)2 (1400 °C, 12 h).
ChemInform Abstract: Luminescence Properties of a New Greenish Blue Emitting Phosphor Na5Ca4(PO4)4F:Eu2+.
Authors: Xiao Haiyi , Xia Zhiguo , Liao Libing , Zhou Jun , Zhuang Jiaqing
Published: August 2012

The new title phosphor is synthesized by solid state reaction of a stoichiometric mixture of Na2CO3, NaF, CaCO3, (NH4)2HPO4, and Eu2O3 under CO reducing atmosphere (alumina crucible, 1000 °C, 4 h).
ChemInform Abstract: CsSnI3: Semiconductor or Metal? High Electrical Conductivity and Strong Near‐Infrared Photoluminescence from a Single Material. High Hole Mobility and Phase‐Transitions.
Authors: Chung In , Song Jung‐Hwan , Im Jino , Androulakis John , Malliakas Christos D. , Li Hao , Freeman Arthur J. , Kenney John T. , Kanatzidis Mercouri G.
Published: August 2012

Single‐crystal structures of three metastable black polymorphs of CsSnI3 are determined for the first time.
ChemInform Abstract: Systematic Evolution from Uranyl(VI) Phosphites to Uranium(IV) Phosphates.
Authors: Villa Eric M. , Marr Connor J. , Jouffret Laurent J. , Alekseev Evgeny V. , Depmeier Wulf , Albrecht‐Schmitt Thomas E.
Published: August 2012

In situ hydrothermal redox reactions of uranyl nitrate with phosphorous acid and alkali metal carbonates are explored and six new uranium phosphites, phosphates, and phosphite/phosphate mixed compounds are synthesized hydrothermally and one uranyl phosphite is obtained at room temperature.
ChemInform Abstract: Allylic C—H Activations Using Cu(II) 2‐Quinoxalinol Salen and tert‐Butyl Hydroperoxide.
Authors: Li Yuancheng , Lee Tae Bum , Wang Tanyu , Gamble Audrey V. , Gorden Anne E. V.
Published: August 2012

The Cu complex promotes the regioselective allylic oxidation of olefins giving various enones such as (II) and (V) in good to high yields.
ChemInform Abstract: Mild and Efficient α‐Chlorination of Carbonyl Compounds Using Ammonium Chloride and Oxone (2KHSO5·KHSO4·K2SO4 ).
Authors: Swamy Peraka , Kumar Macharla Arun , Reddy Marri Mahender , Narender Nama
Published: August 2012

A simple protocol for the monochlorination of ketones (I) and (III) and 1,3‐dicarbonyl compounds (IX) and (XII) utilizing NH4Cl as a source of chlorine and Oxone as an oxidant in MeOH without any catalyst is presented.
ChemInform Abstract: Copper‐Catalyzed Di‐ and Trifluoromethylation of α,β‐Unsaturated Carboxylic Acids: A Protocol for Vinylic Fluoroalkylations.
Authors: He Zhengbiao , Luo Tao , Hu Mingyou , Cao Yanjing , Hu Jinbo
Published: August 2012

The copper reagent and the carboxylic acid group in the substrates play an important role in the new effective protocol for the title synthesis.
ChemInform Abstract: Oxidative Heck Arylation for the Stereoselective Synthesis of Tetrasubstituted Olefins Using Nitroxides as Oxidants.
Authors: He Zhiheng , Kirchberg Sylvia , Froehlich Roland , Studer Armido
Published: August 2012

A mild and highly stereoselective sequential synthesis of the title compounds is developed.
ChemInform Abstract: Experimental and Theoretical Studies on the Nazarov Cyclization/Wagner—Meerwein Rearrangement Sequence.
Authors: Leboeuf David , Gandon Vincent , Ciesielski Jennifer , Frontier Alison J.
Published: August 2012

Highly functionalized cyclopentenones are chemoselectively formed by the copper(II)‐mediated reaction of divinyl ketones.
ChemInform Abstract: An Efficient Synthetic Method for Allyl‐Epoxides via Allylation of α‐Haloketones or Esters with Allylmagnesium Bromide.
Authors: Fan Liyuan , Zhang Min , Zhang Songlin
Published: August 2012

A new, simple, mild, and non‐metal‐catalyzed method for the title synthesis is developed.
ChemInform Abstract: Silver‐Mediated Oxidative C—H/C—H Functionalization: A Strategy to Construct Polysubstituted Furans.
Authors: He Chuan , Guo Sheng , Ke Jie , Hao Jing , Xu Huan , Chen Hongyi , Lei Aiwen
Published: August 2012

An extremely simple and atom‐economic method allows the preparation of trisubstituted furans from 1,3‐dicarbonyl compounds and aryl terminal alkynes in the presence of a stoichiometric amount of silver carbonate.
ChemInform Abstract: A Direct Catalytic Asymmetric Aldol Reaction of α‐Sulfanyl Lactones: Efficient Synthesis of SPT Inhibitors.
Authors: Takechi Sho , Yasuda Shigeo , Kumagai Naoya , Shibasaki Masakatsu
Published: August 2012

The scalable and not moisture sensitive [indicated by the reaction with the compound (IId)] title aldol reaction is developed.
ChemInform Abstract: Solvent‐Free Non‐Covalent Organocatalysis: Enantioselective Addition of Nitroalkanes to Alkylideneindolenines as a Flexible Gateway to Optically Active Tryptamine Derivatives.
Authors: Fochi Mariafrancesca , Gramigna Lucia , Mazzanti Andrea , Duce Sara , Fantini Stefano , Palmieri Alessandro , Petrini Marino , Bernardi Luca
Published: August 2012

Cinchona alkaloid‐catalyzed reaction of a diversity of in situ generated alkylideneindolenines with various nitroalkanes provides access towards polysubstituted nitroethylindoles, e.g. (III), (V), (VII), (IX) and (XI).
ChemInform Abstract: Trienamine Catalysis with 2,4‐Dienones: Development and Application in Asymmetric Diels—Alder Reactions.
Authors: Xiong Xiao‐Feng , Zhou Quan , Gu Jing , Dong Lin , Liu Tian‐Yu , Chen Ying‐Chun
Published: August 2012

The δ,δ‐substitution pattern of the 2,4‐dienones is necessary for the reaction.
ChemInform Abstract: L‐Proline‐Catalyzed Knoevenagel Condensation: A Facile, Green Synthesis of (E)‐Ethyl 2‐Cyano‐3‐(1H‐indol‐3‐yl)acrylates and (E)‐3‐(1H‐Indol‐3‐yl)acrylonitriles.
Authors: Venkatanarayana M. , Dubey P. K.
Published: August 2012

An environmentally friendly Knoevenagel condensation of indolecarboxaldehydes (I) with malonomononitrile (II) is achieved in ethanol using L‐proline as catalyst.
ChemInform Abstract: MCM‐41‐SO3H as a Highly Efficient Sulfonic Acid Nanoreactor for the Rapid and Green Synthesis of Some Novel Highly Substituted Imidazoles under Solvent‐Free Condition.
Authors: Mahdavinia Gholam Hossein , Amani Ali Mohammad , Sepehrian Hamid
Published: August 2012

The applied catalytic system can be recycled several times.
ChemInform Abstract: Achiral Counterion Control of Enantioselectivity in a Broensted Acid‐Catalyzed Iodolactonization.
Authors: Dobish Mark C. , Johnston Jeffrey N.
Published: August 2012

The combination of a chiral ammonium cation and the achiral triflimide anion present in catalyst (I) affords the highest enantioselectivity in the iodolactonization reaction of acid (IIa) compared to eight other combinations of the cation with achiral sulfonate counterions.
ChemInform Abstract: Organocatalytic Enantioselective Michael Addition of a Kojic Acid Derivative to Nitro Olefins.
Authors: Wang Jiyu , Zhang Qing , Zhang Hui , Feng Yujun , Yuan Weicheng , Zhang Xiaomei
Published: August 2012

The e.e.
ChemInform Abstract: Palladium‐Catalyzed Cycloaddition of Alkynyl Aryl Ethers with Internal Alkynes via Selective ortho C—H Activation.
Authors: Minami Yasunori , Shiraishi Yuki , Yamada Kotomi , Hiyama Tamejiro
Published: August 2012

Silylalkynyl aryl ethers and internal alkynes give under optimized conditions silylmethylidene‐substituted chromenes.
ChemInform Abstract: Modulating the Reactivity of Functionalized N,S‐Ketene Acetal in MCR: Selective Synthesis of Tetrahydropyridines and Thiochromeno[2,3‐b]pyridines via DABCO‐Catalyzed Tandem Annulation.
Authors: Wen Li‐Rong , Shi Yong‐Jie , Liu Guang‐Yuan , Li Ming
Published: August 2012

A variety of pharmacologically interesting heterocyclic scaffolds is available via the three‐component process under optimized conditions A).
ChemInform Abstract: One Pot Synthesis of Medicinally Important cis‐2‐Methyl‐4‐amino Substituted‐1,2,3,4‐tetrahydroquinolines.
Authors: Kiran Kumar H. C. , Mahadevan K. M. , Prabhakara Varma P. , Srinivasa A.
Published: August 2012

Antimony trichloride is an efficient catalyst for the synthesis of cis‐tetrahydroquinolines (III) and (V) by reaction of anilines (I) with N‐vinylcaprolactam (II) or N‐vinylcarbazole (IV), respectively.
ChemInform Abstract: A New Cascade Reaction: Concurrent Construction of Six and Five Membered Rings Leading to Novel Fused Quinazolinones.
Authors: Kumar K. Siva , Kumar P. Mahesh , Rao V. Sreenivasa , Jafar Ahamed A. , Meda Chandana Lakshmi T. , Kapavarapu R. , Parsa Kishore V. L. , Pal Manojit
Published: August 2012

The compounds (IV) are evaluated in vitro for their inhibitory potential against phosphodiesterase 4.
ChemInform Abstract: Stereocontrol in a Combined Allylic Azide Rearrangement and Intramolecular Schmidt Reaction.
Authors: Liu Ruzhang , Gutierrez Osvaldo , Tantillo Dean J. , Aube Jeffrey
Published: August 2012

In the presence of a Lewis acid, an interconverting set of isomeric allylic azides undergoes the Schmidt reaction to afford substituted lactams stereoselectively.
ChemInform Abstract: Enantioselective Synthesis of ε‐Lactones by Lipase‐Catalyzed Resolution.
Authors: Shimotori Yasutaka , Aoyama Masakazu , Tsukasa Hidetaka , Miyakoshi Tetsuo
Published: August 2012

Enantioenriched lactone (V) is prepared by a sequence of lipase‐catalyzed kinetic resolution, alkaline hydrolysis and Novozym 435‐catalyzed lactonization.
ChemInform Abstract: Cross‐Coupling Between sp3‐Carbon and sp3‐Carbon Using a Diborylmethane Derivatives at Room Temperature.
Authors: Endo Kohei , Ohkubo Takahiro , Ishioka Takafumi , Shibata Takanori
Published: August 2012

The new and efficient method allows access to homoallylboronates and arylethylboronates.
ChemInform Abstract: Synthesis and Biological Evaluation of Oleanolic Acid Derivatives as Novel Inhibitors of Protein Tyrosine Phosphatase 1B.
Authors: Li Hui , Zou Hui , Gao Lixin , Liu Ting , Yang Fan , Li Jingya , Li Jia , Qiu Wen‐Wei , Tang Jie
Published: August 2012

A series of novel oleanolic acid derivatives with five‐membered heterocyclic rings, fused at the C‐2, C‐3 positions, e.g. (II) and (V), as well some C‐ring modified derivatives, e.g. (I), (III) and (IV), is synthesized.
ChemInform Abstract: Synthesis and Biological Activity of Bi/tricyclic Azasugars Fused Thiazolidin‐4‐one and Thiazinan‐4‐one by Microwave‐Assisted Tandem Staudinger/Aza‐Wittig/Cyclization.
Authors: Li Xiaoliu , Qin Zhanbin , Yang Tianyu , Zhang Hongzhi , Wei Sinan , Li Chunxiao , Chen Hua , Meng Ming
Published: August 2012

A series of novel bi‐ and tricyclic azasugars is synthesized.
ChemInform Abstract: Environmentally Benign Synthesis of Sugar Orthoesters Promoted by Anhydrous Sodium Acetate and Ultrasound.
Authors: Zhao Jinzhong , Wei Shanqiao , Yue Aiqin , Shao Huawu
Published: August 2012

By means of ultrasound irradiation, it is possible to reduce the reaction time significantly.
ChemInform Abstract: Intercalation Chemistry of Layered Vanadyl Phosphate: A Review
Authors: Benes Ludvik , Melanova Klara , Svoboda Jan , Zima Vitezslav
Published: August 2012

Review: 182 refs.
ChemInform Abstract: Transition Metal Mediated Cleavage and Activation of C—C Single Bonds
Authors: Ruhland Klaus
Published: August 2012

Review: ca. 200 refs.
ChemInform Abstract: Chiral Synthesis of Iminosugars
Authors: Takahata Hiroki
Published: August 2012

Review: 138 refs.
ChemInform Abstract: Synthetic and Semi‐Synthetic Chondroitin Sulfate Oligosaccharides, Polysaccharides, and Glycomimetics
Authors: Bedini Emiliano , Parrilli Michelangelo
Published: August 2012

Review: 81 refs.
ChemInform Abstract: Redox Properties of Radicals
Authors: Magri David C. , Workentin Mark S.
Published: August 2012

Review: 141 refs.
ChemInform Abstract: Radical Rearrangements: Ester‐Substituted Radicals and Hydrogen Atom Migrations
Authors: Sasaki Kaname , Cumpstey Ian , Crich David
Published: August 2012

Review: 117 refs.
ChemInform Abstract: Basic Concepts on Radical Chain Reactions
Authors: Sherburn Michael S.
Published: August 2012

Review: 34 refs.
ChemInform Abstract: Synthetic Clathrate Systems
Authors: Bishop Roger
Published: August 2012

Review: 169 refs.
ChemInform Abstract: Carcerands and Hemicarcerands
Authors: Warmuth Ralf
Published: August 2012

Review: 189 refs.
ChemInform Abstract: Efficient Nonlinear Optical Properties of Dyes Confined in Interlayer Nanospaces of Clay Minerals
Authors: Suzuki Yasutaka , Tenma Yuta , Nishioka Yukihiro , Kawamata Jun
Published: August 2012

Review: 45 refs.
ChemInform Abstract: Magnetic and Porous Molecule‐Based Materials
Authors: Roques Nans , Mugnaini Veronica , Veciana Jaume
Published: August 2012

Review: 245 refs.
ChemInform Abstract: Perspective of Industry on Modeling Catalysis
Authors: Rostrup‐Nielsen Jens R.
Published: August 2012

Review: 53 refs.
ChemInform Abstract: Rapid Multidimensional NMR: Decomposition Methods and Their Applications
Authors: Billeter Martin , Staykova Doroteya K.
Published: August 2012

Review: 30 refs.
ChemInform Abstract: Multidimensional NMR by Projection‐Reconstruction
Authors: Freeman Ray , Kupce Eriks
Published: August 2012

Review: 9 refs.
ChemInform Abstract: Multidimensional Spectroscopy: Concepts
Authors: Ernst Richard R.
Published: August 2012

Review: 67 refs.
Interim analysis of clinical trials based on urn models
Authors: ZHU Hongjian , HU Feifang
Published: August 2012

Clinical trials usually involve efficient and ethical objectives such as maximizing the power and minimizing the total failure number. Interim analysis is now a standard technique in practice to achieve these objectives. Randomized urn models have been extensively studied in the literature. In this paper, we propose to perform interim analysis on clinical trials based on urn models and study its properties. We show that the urn composition, allocation of patients and parameter estimators can be approximated by a joint Gaussian process. Consequently, sequential test statistics of the proposed procedure converge to a Brownian motion in distribution and the sequential test statistics asymptotically satisfy the canonical joint distribution defined in Jennison & Turnbull (Jennison & Turnbull 2000. Group Sequential Methods with Applications to Clinical Trials, Chapman and Hall/CRC). These results provide a solid foundation and open a door to perform the interim analysis on randomized clinical trials with urn models in practice. Furthermore, we demonstrate our proposal through examples and simulations by applying sequential monitoring and stochastic curtailment techniques. The Canadian Journal of Statistics 40: 550–568; 2012 © 2012 Statistical Society of Canada
Information borrowing methods for covariate‐adjusted ROC curve
Authors: GUAN Zhong , QIN Jing , ZHANG Biao
Published: August 2012

In medical diagnostic testing problems, the covariate adjusted receiver operating characteristic (ROC) curves have been discussed recently for achieving the best separation between disease and control. Due to various restrictions such as cost, the availability of patients, and ethical issues quite frequently only limited information is available. As a result, we are unlikely to have a large enough overall sample size to support reliable direct estimations of ROCs for all the underlying covariates of interest. For example, some genetic factors are less commonly observable compared with others. To get an accurate covariate adjusted ROC estimation, novel statistical methods are needed to effectively utilize the limited information. Therefore, it is desirable to use indirect estimates that borrow strength by employing values of the variables of interest from neighbouring covariates. In this paper we discuss two semiparametric exponential tilting models, where the density functions from different covariate levels share a common baseline density, and the parameters in the exponential tilting component reflect the difference among the covariates. With the proposed models, the estimated covariate adjusted ROC is much smoother and more efficient than the nonparametric counterpart without borrowing information from neighbouring covariates. A simulation study and a real data application are reported.The Canadian Journal of Statistics40: 569–587; 2012 © 2012 Statistical Society of Canada
Covalent Triazine Frameworks as Heterogeneous Catalysts for the Synthesis of Cyclic and Linear Carbonates from Carbon Dioxide and Epoxides
Authors: Roeser Jérôme , Kailasam Kamalakannan , Thomas Arne
Published: August 2012

The base catalytic properties of a series of triazine‐based covalent organic frameworks were evaluated for the conversion of CO2 to organic carbonates. The high number of basic nitrogen sites of the as‐synthesized frameworks efficiently catalyzed the formation of cyclic carbonates via the cycloaddition of CO2 to different starting epoxides. The structural and chemical tunability of the covalent triazine frameworks allowed the fine evaluation of key parameters influencing the observed catalytic activities. An increased surface area and presence of additional mesopores dramatically enhance the activity of the investigated catalytic materials. The chemical composition was also found to influence the reaction, as evidenced by an increased activity at lower reaction temperatures, when a more basic, pyridine‐based, framework was used as catalyst. Finally, the activity in the two‐step cycloaddition/transesterification catalysis of dimethyl carbonate was evaluated in a one‐batch process.
Bio‐oil Deoxygenation by Catalytic Pyrolysis: New Catalysts for the Conversion of Biomass into Densified and Deoxygenated Bio‐oil
Authors: Sanna Aimaro , Andrésen John M.
Published: August 2012

This work proposes an innovative catalytic pyrolysis process that converts bio‐refinery residues, such as spent grains, into intermediate bio‐oil with improved properties compared to traditional bio‐oils, which allows the use of existing crude‐oil refinery settings for bio‐oil upgrading into fuels. The integration of bio‐oil into a crude‐oil refinery would decrease the economic disadvantage of biomass compared to fossil fuels. The catalytic pyrolysis was able to produce bio‐oil with a lower O and N content and high levels of aliphatics and H by using activated serpentine and olivine at 430–460 °C. The activated materials seem to be beneficial to the bio‐oil energy content by increasing it from less than 20 MJ kg−1 in the original biomass to 26 MJ kg−1. Approximately 70–74 % of the starting energy remains in the bio‐oil using activated olivine (ACOL) and activated serpentine (ACSE) at 430 °C, whereas only 52 % is retained using alumina (ALU) at the same temperature. There was a strong reduction of the O content in the bio‐oils, and the deoxygenation power decreased in the following order: ACOL>ACSE>ALU. In particular, ACOL at 430–460 °C was able to reduce the O content of the bio‐oil by 40 %. The oxygenated bio‐oil macromolecules interact in the catalyst’s active sites with the naturally present metallic species and undergo decarboxylation with the formation of C5–C6 O‐depleted species.
Photocatalytic thin Films Prepared by Plasma Curing of Non‐Reactive Siloxane Dispersions Containing TiO2 Particles
Authors: Ott M. , Dölle C. , Danilov V. , Hartwig A. , Meichsner J. , Salz D. , Schmüser C. , Schorsch O. , Sebald M. , Wagner H.‐E. , Vissing K.‐D.
Published: August 2012

Photocatalytic TiO2 layers prepared by PVD or CVD processes are already produced industrially. The deposited TiO2 needs a sufficiently high concentration of the photocatalytically active anatase phase which is produced at higher substrate temperature. As a consequence, the PVD/CVD techniques are limited to heat‐resistant substrates. A novel approach for plasma hybrid coating technology is presented here using the advantages of a cold low‐pressure plasma process in combination with non‐reactive siloxane (polydimethylsiloxane – PDMS) dispersions containing sub‐micron TiO2 particles for surface functionalisation. As the result, a mechanically stable composite film containing TiO2 particles with a diameter of up to several times the average coating thickness is generated. The film consists of a top SiO2‐like surface layer and, depending on the initial film thickness, an underlying gradually demethylated and crosslinked siloxane. Although the TiO2 particles are partially covered by a thin matrix layer of several nanometres, the thin coating shows photocatalytic activity as demonstrated by UV‐degradation of methylene blue. The photocatalytic activity depends on the TiO2 particle concentration in the film and can be further enhanced by exposing the TiO2 surface by CF4 plasma etching of the composite film (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Comparison of (Cr0.75Al0.25)N Coatings Deposited by Conventional and High Power Pulsed Magnetron Sputtering
Authors: Bagcivan N. , Bobzin K. , Theiß S.
Published: August 2012

Pulsed high power plasma discharges offer high potential by means of developing new coating systems with out‐standing characteristics and enhanced application possibilities. To get high‐performance materials the plasma physics of sputtering, transport and deposition during a High Power Pulse Magnetron Sputtering (HPPMS) process have to be investigated and correlated to coating characteristics as well as compound and system char‐acteristics. Every coating has to be adapted to the specific application which it addresses. In the frame of this research project the HPPMS technology is used to investigate coating systems regarding their possibility to be used in injection molding processes.

This manuscript shows a first comparison of conventional sputtered ternary Cr‐Al‐N by direct current (DC) magnetron sputtering (MS), pulsed middle frequency (MF) MS and Cr‐Al‐N deposited by HPPMS. The Cr:Al ratio was kept constant at about 75: 25 (at‐%). All three coatings were analyzed regarding thickness, morphology, chemical composition, texturing and mechanical properties like hardness and Young's modulus. Furthermore, all three coatings were deposited on the complex structure of a gear wheel to obtain the uniformity of the coating.

The results show that coatings cannot provide outstanding advantages regarding mechanical properties or advantages in morphology compared to conventionally deposited coatings. However, HPPMS shows a completely different phase texturing measured by X‐ray diffraction and a better uniformity on complex components (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Microwave Plasma Sources ‐Applications in Industry
Authors: Kaiser M. , Baumgärtner K.‐M. , Mattheus A.
Published: August 2012

Plasma, excited with microwave energy, has very interesting properties which are in direct correlation with the excitation frequency. This is due to the reachable high electron density, which itself has an influence on the density of further generated particles like ions, radicals, excited atoms and molecules or UV light. Altogether they are responsible for the high chemical reactivity of microwave plasmas attaining their maximum in the pressure regime between 1 and a few hundred Pa. Therefore, comparatively low end pumping systems can be used to achieve good results in etching, activation and deposition processes. Together with the availability of microwave generators, grown with the market of microwave heating technology, microwave plasma is an interesting tool for industrial applications. Scalability of power up to 100 kW per single magnetron tube and lateral dimensions of a few square meters per single plasma source have opened the field to industrial thin film technology for typical large area applications as solar or other flat panel industries.

Roth & Rau Muegge is utilizing these advantages to supply microwave generators and plasma technology for various fields of applications which will be provided as an overview to give insight into running activities in industry. Although the presented applications are part of publicly funded programs and projects together with partners from several research institutes and universities, the technical depth of this contribution has to consider running contracts and non disclosure agreements (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Objectives of Laser‐Induced Energy Deposition for Active Flow Control
Authors: Sperber D. , Eckel H.‐A. , Steimer S. , Fasoulas S.
Published: August 2012

A highly concentrated energy deposition has been proposed for a flow control concept in super‐ and hypersonic transportation. The plasma source can be implemented by laser‐, microwave‐ or DC‐discharge phenomena in the flow field upstream of a blunt body. In a wide range of Mach numbers the thermal modification of the gas condition mitigates the strength of the shock waves and improves the aerodynamic performance. This paper presents a discussion of the methodology and objectives of laser‐induced energy deposition particularly with regard to the generation of laser‐sustained plasma in supersonics. A steady‐state argon plasma is maintained by an intensity field in the focal region of a continuous wave laser. The experimental results using drag, laser energy transmission and plasma radiation measurements determine the requirements for laser‐sustained plasma and validate the control authority of this concept (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Plasma Health Care ‐ Old Problems, New Solutions
Authors: Morfill G. E. , Zimmermann J. L.
Published: August 2012

This paper tries to focus on pertinent issues in health care and analyses how cold atmospheric plasmas can contribute towards the long‐standing problems identified. It starts quite generally by looking at the major elements that make up our current health care system, the aims that govern these and the corresponding requirements on health care products. It then proceeds to identify areas where current research promises contributions from the new cold plasma technologies. It turns out that there are indeed many areas where investments in plasma health care could pay off, both in terms of cost and in reduction of human suffering (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
User‐defined protein marker assay development for characterization of circulating tumor cells using the CellSearch® system
Authors: Lowes Lori E. , Hedley Benjamin D. , Keeney Mike , Allan Alison L.
Published: August 2012

The majority of cancer‐related deaths result from metastasis, which has been associated with the presence of circulating tumor cells (CTCs). It has been shown that CTC cut‐off values exist that predict for poorer overall survival in metastatic breast (≥5), prostate (≥5), and colorectal (≥3) cancer based on assessment of 7.5 ml of blood. Development of the CellSearch® system (Veridex) has allowed for sensitive enumeration of CTCs. In the current study, protocols were developed and optimized for use with the CellSearch system to characterize CTCs with respect to user‐defined protein markers of interest in human blood samples, including the cancer stem cell marker CD44 and the apoptosis marker M‐30. Flow cytometry (FCM) experiments were initially carried out to assess expression of CD44 and M‐30 on MDA‐MB‐468 human tumor cells. Human blood samples were then spiked with MDA‐MB‐468 cells and processed with the appropriate antibody (CD44/M‐30) on the CellSearch. Detailed optimization of CD44 was carried out on the CellSearch using various antibody concentrations, exposure times, and cell lines with varying CD44 expression. Troubleshooting experiments were undertaken to explain observed discrepancies between FCM and CellSearch results for the M‐30 marker. After extensive optimization, the best CD44/M‐30 concentrations and exposure times were determined to be 1.5/3.5 μg/ml and 0.2/0.8 s, respectively. The percentage of CD44+ tumor cells was 99.5 ± 0.39% by FCM and 98.8 ± 0.51% by the CellSearch system. The percentage of M‐30+ tumor cells following paclitaxel treatment was 17.6 ± 1.18% by FCM and 10.9 ± 2.41% by CellSearch. Proper optimization of the CD44 marker was achieved; however, M‐30 does not appear to be a suitable marker for use in this platform. Taken together, the current study provides a detailed description of the process of user‐defined protein marker development and optimization using the CellSearch, and will be an important resource for the future development of protein marker assays by users of this platform. © 2012 International Society for Advancement of Cytometry
Regioselective Synthesis of Alkylarenes by Two‐Step ipso‐Substitution of Aromatic Dicarboxylic Acids
Authors: Bramborg Andrea , Linker Torsten
Published: August 2012

A strategy for the regioselective alkylation of arenes was developed, starting from commercially available and inexpensive terephthalic acid or naphthalene‐1,4‐dicarboxylic acid. The method entails a formal ipso‐substitution of the carboxylate groups by a sequence of reductive alkylation under Birch conditions and subsequent acid‐mediated rearomatization with loss of carbon monoxide and carbon dioxide. More than 20 different arenes with various side‐chains were synthesized. With naphthalene‐1,4‐dicarboxylic acid as starting material, we were able to control the degree of alkylation by choosing the appropriate electrophile in the Birch reduction. Thus, bisalkylated naphthalenes and naphthoic acids became available chemoselectively. All reactions afforded a single regioisomer exclusively in high yields. Overall, aromatic dicarboxylic acids are suitable substrates for a two‐step ipso‐substitution that allows the selective synthesis of alkylated benzenes and naphthalenes.
One‐Pot, Three‐Component Synthesis of 1,4,5‐Trisubstituted 1,2,3‐Triazoles Starting from Primary Alcohols
Authors: Jin Guanyi , Zhang Jian , Fu Dan , Wu Jingjing , Cao Song
Published: August 2012

A novel, one‐pot, three‐component approach for the synthesis of 1,4,5‐trisubstituted 1,2,3‐triazoles through the cycloaddition of a wide range of primary alcohols with sodium azide and active methylene ketones in the presence of N‐(p‐toluenesulfonyl)imidazole, tetrabutylammonium iodide, and triethylamine in DMF/DMSO has been developed.
Modeling of a large‐scale magneto‐rheological damper for seismic hazard mitigation. Part II: Semi‐active mode
Authors: Chae Yunbyeong , Ricles James M. , Sause Richard
Published: August 2012

A magneto‐rheological (MR) damper is a semi‐active device where the damper force capacity is controlled by varying the input current into the damper. In this paper, the dynamics of MR dampers associated with variable current input is studied. Electromagnetic theory is used to model the dynamics of an MR damper including the eddy current effect and the nonlinear hysteretic behavior of damper material magnetization. A nonlinear differential equation that relates the input current to the damper with a constant equivalent current is proposed. The nonlinear differential equation is combined with the Maxwell Nonlinear Slider (MNS) model to create the variable current MNS model to predict the damper force under variable input current and random damper displacement loading. The model is evaluated by comparing the predicted response of a large‐scale MR damper to the measured damper response from experiments. The experiments include a real‐time hybrid simulation of a 3‐story building structure with a large‐scale MR damper subjected to the design earthquake. The exceptional agreement observed between the predicted and experimental results illustrate the robustness and the accuracy of the variable current MNS model. Copyright © 2012 John Wiley & Sons, Ltd.
Natural gas production—international/cross‐border: Rest of world learning from US shale gas experience
Authors: Sakmar Susan L.
Published: August 2012

Canada has significant petroleum, natural gas, and coal reserves and is one of only three member‐states of the Organisation for Economic Co‐operation and Development (OECD) that is a net energy exporter.1 Canada is the largest source of US energy imports, and nearly all of Canada's oil and gas exports go to the United States. Recognizing the importance of energy trade, both the United States and Canada, along with Mexico, participate in the North American Energy Working Group, which seeks to improve energy integration and cooperation between the countries in the region.2
Gas and electric transmission: Right‐of‐way acquisition surveys and elements critical to acquisition process
Authors: Hart James M. (Mike)
Published: August 2012

The acquisition of rights to construct, operate, and maintain a linear facility such as an overhead electric transmission line or an underground gas or petroleum pipeline involves many players. Initial contact with landowners (the grantor as well as those unaffected by the corridor) is most often made by the right‐of‐way (ROW) acquisition specialist or negotiator for the purpose of acquiring right of entry (ROE) to perform surveys for engineering design, geotechnical analysis, and environmental studies. Field surveys for engineering design are often conducted in conjunction with land ties for the preparation of legal descriptions and plats/exhibits for the acquisition of rights necessary to the project.
Regulatory economics: The best defense for fracking is a good offense
Authors: Barclay Richard A.
Published: August 2012

Fracking (hydraulic fracturing) production of natural gas has moved out of the background. In just a few years, it has gone from half a dozen states to nationwide.