bluuebunny/crossref_metadata_2025 huggingface dataset:
Three‐Dimensional Concentration Mapping of Organic Blends
Authors: Roehling John D. , Batenburg K. Joost , Swain F. Benjamin , Moulé Adam J. , Arslan Ilke
Published: November 2012

The three‐dimensional morphology of mixed organic layers are quantitatively measured using high‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM) with electron tomography for the first time. The mixed organic layers used for organic photovoltaic applications have not been previously imaged using STEM tomography as there is insufficient contrast between donor and acceptor components. Contrast is generated by substituting fullerenes with endohedral fullerenes that contain a Lu3N cluster within the fullerene cage. The high contrast and signal‐to‐noise ratio, in combination with use of the discrete algebraic reconstruction technique (DART), allows generation of the most detailed and accurate three‐dimensional map of BHJ morphology to date. From the STEM‐tomography reconstructions it is determined that three distinct material phases are present within the BHJs. By observing changes to morphology and mixing ratio during thermal and solvent annealing, the effects of mutual solubility and fullerene crystallization on morphology and long term stability are determined. This material/technique combination shows itself as a powerful tool for examining morphology in detail and allows for observation of nanoscopic changes in local concentration.
Hepcidin levels predict nonresponsiveness to oral iron therapy in patients with iron deficiency anemia
Authors: Bregman David B. , Morris David , Koch Todd A. , He Andy , Goodnough Lawrence T.
Published: November 2012

Levels of hepcidin, a major regulator of iron homeostasis, may identify patients with iron deficiency anemia (IDA) who will not respond to oral iron therapy. In this study, IDA patients underwent a 14‐day trial (run‐in) course of ferrous sulfate therapy. Nonresponders (Hgb increase <1 g/dL with 67% compliance rate) were randomized to IV ferric carboxymaltose (FCM; two injections of 750 mg) or further oral iron for 14 days. Screening hepcidin levels were 38.4 versus 11.3 ng/mL, P = 0.0002 in nonresponders versus responders to a trial of oral iron. Hepcidin of > 20 ng/mL, showed sensitivity of 41.3%, specificity of 84.4%, and positive predictive value of 81.6% for predicting nonresponsiveness to oral iron. PPVs for ferritin> 30 ng/mL or transferrin saturation (TSAT)>15% were 59.2 and 55%, respectively. Negative predictive values for hepcidin, ferritin, and TSAT were 46.3, 22.7, and 19.7, respectively. FCM versus oral iron showed Hgb increases of ≥1 gm/dL in 65.3% versus 20.8% (P < 0.0001) and Hgb increases of 1.7 ± 1.3 versus 0.6 ± 0.9 g/dL (P = 0.0025), respectively. We conclude that hepcidin predicts nonresponsiveness to oral iron in patients with IDA and is superior to TSAT or ferritin for this purpose. Nonresponse to oral iron therapy does not rule out IDA, since two‐thirds of patients subsequently responded to intravenous iron. Am. J. Hematol. 88:97–101, 2013. © 2012 Wiley Periodicals, Inc.
Baseline serum TARC levels predict therapy outcome in patients with Hodgkin lymphoma
Authors: Sauer Maike , Plütschow Annette , Jachimowicz Ron D. , Kleefisch Dominik , Reiners Katrin S. , Ponader Sabine , Engert Andreas , von Strandmann Elke Pogge
Published: November 2012

Hodgkin lymphoma (HL) has become one of the best curable cancers. However, better biomarkers are needed for outcome prediction that would allow protecting patients from over‐ or under‐dosing of treatment. Thymus and activation‐regulated chemokine/CCL17 (TARC) is highly and specifically elevated in this disease and has been proposed as possible biomarker in HL patients. In this study, we show that pretreatment TARC levels were associated with established clinical risk factors and predictive for response to treatment in a large cohort of HL patients treated in clinical trials by the German Hodgkin Study Group. Moreover, TARC levels also significantly contributed to a novel multivariate model predicting treatment response. These data clearly suggest an important role for this chemokine as biomarker in HL. Am. J. Hematol. 88:113–115, 2013. © 2012 Wiley Periodicals, Inc.
Increased risk of breast cancer in women with NF1
Authors: Madanikia Sara Aileen , Bergner Amanda , Ye Xiaobu , Blakeley Jaishri O'Neill
Published: November 2012

Neurofibromatosis type 1 (NF1) is a common autosomal dominant disorder associated with increased risk for neoplasms. Two studies in the United Kingdom have indicated that women with NF1 (particularly women under 50) may also be at increased risk of breast cancer. No such study has been done to date in the United States. Chart review for breast cancer diagnoses was undertaken for 126 women with NF1 followed at Johns Hopkins who were 20 years of age or older. Four of 126 women who met eligibility criteria were diagnosed with breast cancer (3.2% over 15 years). The unadjusted standardized incidence ratio (SIR) for breast cancer in the NF1 population between the ages of 20 and 49 was 2.68 (P = 0.076, 95% CI 0.68–7.29) based on incidence rates of breast cancer in the general population taken from the Surveillance Epidemiology and End Results (SEER) database. The unadjusted SIR for women with NF1 ≥50 was 0.81 (P = 0.84, 95% CI 0.041–4.01). When adjusted for race, the rate of NF1 in the general population and time of diagnosis, the SIR was 4.41 (P = 0.0049, 95% CI 1.12–12.00) for women <50 versus 0.94 (P = 0.95, 95% CI 0.047–4.65) for women ≥50. The trend of a higher‐than‐expected number of breast cancer cases in women <50 with NF1 agrees with the prior studies from the literature. Cumulatively, the data suggests an increased risk of breast cancer for women with NF1 < 50 years old, implying a need for closer surveillance and the establishment of screening guidelines for this patient population. © 2012 Wiley Periodicals, Inc.
N‐Methylation of Peptides and Proteins: An Important Element for Modulating Biological Functions
Authors: Chatterjee Jayanta , Rechenmacher Florian , Kessler Horst
Published: November 2012

N‐Methylation is one of the simplest chemical modifications often occurring in peptides and proteins of prokaryotes and higher eukaryotes. Over years of evolution, nature has employed N‐methylation of peptides as an ingenious technique to modulate biological function, often as a mode of survival through the production of antibiotics. This small structural change can not only mobilize large protein complexes (as in the histone methylation), but also inhibits the action of enzymes by selective recognition of protein–protein interaction surfaces. In recent years through the advancement in synthetic approaches, the potential of N‐methylation has begun to be revealed, not only in modulating biological activity and selectivity as well as pharmacokinetic properties of peptides, but also in delivering novel drugs. Herein, we summarize the current knowledge of the versatility of N‐methylation in modulating biological, structural, and pharmacokinetic properties of peptides.
Production of 3D scaffolds applied to tissue engineering using chitosan swelling as a porogenic agent
Authors: Mendonça Roberta Helena , de Oliveira Meiga Taíla , da Costa Marysilvia Ferreira , da Silva Moreira Thiré Rossana Mara
Published: November 2012

The preparation of 3D scaffolds using poly(3‐hydroxybutyrate) (PHB) and chitosan (CTS) has been proposed because of the favorable interactions of these materials with mammalian cells in particular osteoblasts (HOB). In this work, a new method of producing porous 3D scaffolds based on the swelling of a dense matrix of PHB and CTS was developed. Scanning electron microscopy images showed the formation of an interconnected porous CTS structure inside a PHB structure. The pore formation was attributed to the swelling of CTS. The scaffolds presented 70% porosity, heterogeneous pore‐size distribution, and a compressive modulus equal to (13.07 ± 0.014) MPa, which is close to that of cancellous bone. In vitro cytotoxicity assays indicate that the scaffold was not cytotoxic. Its morphology, chemical, and physical properties indicate that the scaffold produced by this new methodology has potential applications in bone‐tissue engineering, with drug‐delivery capabilities. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Thermorheological behavior analysis of mLLDPE and mVLDPE: Correlation with branching structure
Authors: Dordinejad A. K. , Jafari S. H. , Khonakdar H. A. , Wagenknecht U. , Heinrich G.
Published: November 2012

In this article, the correlation between the thermorheological behavior and the molecular structure of two grades of metallocene polyethylene, namely linear low density and very low density polyethylene, is studied. The investigated polymers possess the same molecular weight and polydispersity index, but different levels of short branches. Increasing the number of short branches results in enhanced activation energy and delayed relaxation times of the polymers. Four methods including the time–temperature superposition (TTS), van Gurp‐Palmen and activation energy (Ea) as a function of the phase angle, Ea(δ), and the storage modulus, Ea(G′) are employed to study the thermorheological behavior of the samples. The results indicated that the thermorheologically simple behavior is dominant in the specimens. Both the Ea(δ) and Ea(G′) showed independency toward phase angle and the storage modulus. Moreover, the activation energy values obtained from the TTS principle and the Ea(δ) and Ea(G′) diagrams were in good agreement. The zero‐shear rate viscosity of the samples also followed the equation of the linear polyethylene. Regarding the simple thermorheological behavior and the agreement of the zero shear rate viscosity with the relation of the linear polyethylene, one can conclude that long branches do not exist in the investigated metallocene polyethylenes of this article. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Nanocomposite piezoelectric films of P(VDF‐TrFE)/LiNbO3
Authors: Nguyen Van Son , Badie Laurent , Lamouroux Emmanuel , Vincent Brice , Santos Fabrice Domingues Dos , Aufray Maëlen , Fort Yves , Rouxel Didier
Published: November 2012

Piezoelectric films were prepared by incorporation of lithium niobate (LiNbO3) nanoparticles into copolymer of vinylidene difluoride and trifluoroethylene. Nanoparticles of LiNbO3 with ferroelectric phase were successfully synthesized and dispersed homogenously by ultrasonication in the copolymer matrix without any surfactant or surface functionalization. The nanocomposites were fully characterized by electronic microscopy, X‐ray diffraction, differential scanning calorimetry, dynamical mechanical analysis, and piezometer. Surprisingly, the copolymer matrix crystallinity and morphology were not affected by the incorporation of nanoparticles. Therefore the nanocomposites remained good mechanicals properties and high ferroelectricity coupled to nonlinear optical activity thanks to the noncentro symmetric space group of lithium niobate. This could be a novel approach to develop new multifunctional materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Natural weather, soil burial and sea water ageing of low‐density polyethylene: Effect of starch/linear low‐density polyethylene masterbatch
Authors: Elanmugilan M. , Sreekumar P. A. , Singha N. K. , Al‐Harthi Mamdouh A. , De S. K.
Published: November 2012

Degradation of the blends of low‐density polyethylene (LDPE) with a starch‐based additive namely, polystarch N was studied under various environmental conditions such as natural weather, soil and sea water in Saudi Arabia. Stress–strain properties and thermal behavior were investigated for the LDPE and LDPE/polystarch N blend having 40% (w/w) of polystarch N. Environmental ageing resulted in the reduction of percentage of elongation and crystallinity for the blend. Rheological studies and scanning electron microscope photomicrographs of the polymer samples retrieved after ageing showed that addition of polystarch N enhanced the degradation of LDPE. This is ascribed to high extent of chain scission and leaching out of starch present in polystarch N, which was corroborated by the results of morphology and Fourier transform infrared spectroscopy analyses. In the case of underground soil ageing, microbes present in the soil consume the starch in the blend, thus accelerating the degradation process. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Morphogenesis of the Manubrium of Sternum in Human Embryos: A New Concept
Authors: Rodríguez‐Vázquez José Francisco , Verdugo‐López Samuel , Garrido Jose Manuel , Murakami Gen , Kim Ji Hyun
Published: November 2012

To revisit many theories on fetal development of the manubrium of the sternum, we examined 25 mid‐term fetuses at 6–9 weeks of gestation. The initial developmental stage of the manubrium was characterized by a distinct interclavicular mesenchyme that was continuous with the developing clavicles. Because parts of the clavicle in which endochondral ossification occurs originate from the neural crest, the interclavicular mesenchyme seems to be of the same origin. The sternal bands, possibly of the lateral plate origin, were restricted at the anterior ends of the ribs in the paired thoracic walls. The interclavicular mesenchyme extended caudally and laterally to reach the anterior ends of the first ribs, and thus the interclavicular mesenchyme expanded into the intercostoclavicular mesenchyme. Then, the primitive manubrium was delimited by the sternoclavicular joint and its related ligaments, all of which developed from the interclavicular and intercostoclavicular mesenchymes. Although the first ribs were attached to the intercostoclavicular mesenchyme, the former was vimentin‐negative in contrast to the latter, positive mesenchyme. Soon afterwards, the small upper end of the sternal bands was integrated into the intercostoclavicular mesenchyme to form the primitive manubrium. The infrahyoid muscles and their supplying nerves maintained a close topographical relation to the interclavicular or intercostoclavicular mesenchyme, whereas the pectoralis major muscle kept attachments to the sternal bands. Consequently, the manubrium of sternum appeared to develop in a complex way at a junction area between derivatives of the neural crest, lateral plate, and somite. Anat Rec, 2013. © 2012 Wiley Periodicals, Inc.
A classification framework for web robots
Authors: Doran Derek , Gokhale Swapna S.
Published: November 2012

The behavior of modern web robots varies widely when they crawl for different purposes. In this article, we present a framework to classify these web robots from two orthogonal perspectives, namely, their functionality and the types of resources they consume. Applying the classification framework to a year‐long access log from the UConn SoE web server, we present trends that point to significant differences in their crawling behavior.
Exploring the Interaction between Graphene Derivatives and Metal Ions as a Key Step towards Graphene–Inorganic Nanohybrids
Authors: Wang Bin , Song Qi , Luo Bin , Li Xianglong , Liang Minghui , Feng Xinliang , Wagner Manfred , Müllen Klaus , Zhi Linjie
Published: November 2012

The assembly of graphene derivatives and inorganic nanostructures opens up an exciting new field in the functionalization of nanomaterials. However, a better understanding of the interaction between graphene derivatives and inorganic precursors remains a challenge. This work provides an efficient strategy for exploring this interaction by first modifying graphene oxide with aniline, glycine, and glycyl glycine, respectively, and thus engineering the chemical microenvironments on graphene sheets for anchoring metal ions. After that, the affinities of graphene derivatives to various metal ions can be investigated with the help of a conventional electrochemical method. The method highlights the importance of graphene chemistry in hybrid preparation and provides design principles for chemical modifiers used in the construction of multifunctional carbon–inorganic nanostructures.
Increased Glutamate Concentration in the Auditory Cortex of Persons With Autism and First‐Degree Relatives: A 1H‐MRS Study
Authors: Brown Mark S. , Singel Debra , Hepburn Susan , Rojas Donald C.
Published: November 2012

Increased glutamate levels have been reported in the hippocampal and frontal regions of persons with autism using proton magnetic resonance spectroscopy (1H‐MRS). Although autism spectrum disorders (ASDs) are highly heritable, MRS studies have not included relatives of persons with ASD. We therefore conducted a study to determine if glutamate levels are elevated in people with autism and parents of children with autism. Single‐voxel, point‐resolved spectroscopy data were acquired at 3T for left and right hemisphere auditory cortical voxels in 13 adults with autism, 15 parents of children with autism, and 15 adult control subjects. The primary measure was glutamate + glutamine (Glx). Additional measures included n‐acetyl‐aspartate (NAA), choline (Cho), myoinositol (mI), and creatine (Cr). The autism group had significantly higher Glx, NAA, and Cr concentrations than the control subjects. Parents did not differ from control subjects on any measures. No significant differences in Cho or mI levels were seen among groups. No reliable correlations between autism symptom measures, and MRS variables were seen after Bonferroni correction for multiple comparisons. The elevation in Glx in autism is consistent with prior MRS data in the hippocampus and frontal lobe and may suggest increased cortical excitability. Increased NAA and Cr may indicate brain metabolism disturbances in autism. In the current study, we found no reliable evidence of a familial effect for any spectroscopy measure. This may indicate that these metabolites have no heritable component in autism, the presence of a compensatory factor in parents, or sample‐specific limitations such as the participation of singleton families. Autism Res 2012, ●●:●●–●●. © 2012 International Society for Autism Research, Wiley Periodicals, Inc.
Chlorophyll Catabolites in Senescent Leaves of the Lime Tree (Tilia cordata)
Authors: Scherl Mathias , Müller Thomas , Kräutler Bernhard
Published: November 2012

In cold extracts of senescent leaves of the Lime tree (Tilia cordata), two colorless nonfluorescent chlorophyll catabolites (NCCs) were identified, named Tc‐NCC‐1 and Tc‐NCC‐2, as well as a polar yellow chlorophyll catabolite (YCC), named Tc‐YCC. The constitution of the two NCCs was determined by spectroscopic means. In addition, a tentative structure was derived for Tc‐YCC. The three chlorophyll degradation products exhibited tetrapyrrolic structures, as are typical of NCCs or YCCs, and turned out to be rather polar, due to a glucopyranosyl group at their 82‐position. At their 3‐positions, the more polar Tc‐NCC‐1 carried a 1,2‐dihydroxyethyl group and the less polar Tc‐NCC‐2 a vinyl group. Tc‐YCC was identified as the product of an oxidation of Tc‐NCC‐1.
Identification of the Polyhydroxybutyrate Granules in Mammalian Cultured Cells
Authors: Elustondo Pia , Zakharian Eleonora , Pavlov Evgeny
Published: November 2012

Poly‐3‐hydroxybutyrate (PHB) is a biological polyester present in bacteria and eukaryotic cells. Long‐chain (or storage) sPHB (up to 100,000 residues) is typically present in PHB‐accumulating bacteria and localized in specialized granules known as carbonosomes. In these organisms, sPHB plays a major role as carbon and energy storage. On the other hand, short‐chain (or complexed) cPHB (10–100 residues) is present in eukaryotic organisms, including mammals as well as in many bacteria. Previous studies indicated that cPHB is localized in various subcellular compartments of the eukaryotic organisms. Here, we used fluorescent microscopy to directly investigate the localization of PHB in mammalian cells. PHB was visualized in cultured U87 cells using fluorescent probe BODIPY 493/503. Specificity of PHB staining was confirmed by markedly decreased fluorescence of samples treated with PHB‐specific depolymerase (PhaZ7). We found that PHB is associated with granules, and that these PHB‐enriched granules do not co‐localized with mitochondria, lysosomes, or endoplasmic reticulum. These results suggest that, in mammalian cells, PHB can accumulate in the cytoplasm in granules similar to ‘energy storage’ carbonosomes found in PHB‐accumulating bacteria.
New Tripeptide‐Based Macrocyclic Calpain Inhibitors Formed by N‐Alkylation of Histidine
Authors: Chen Hongyuan , Jiao Wanting , Jones Matthew A. , Coxon James M. , Morton James D. , Bickerstaffe Roy , Pehere Ashok D. , Zvarec Ondrej , Abell Andrew D.
Published: November 2012

Two new series of 15‐membered macrocyclic peptidomimetics, in which the P1 and P3 residues of the peptide backbone are linked by a bridge containing a 1,4‐disubstituted 1H‐imidazole, are reported. The structure with an aldehyde at the C‐terminus and the imidazole at P3, i.e., 4c, shows significant inhibitory activity against calpain 2, with an IC50 value of 238 nM. The macrocyclic aldehyde with the imidazole at the alternative P1 position, i.e., 5c, is significantly less active. The relative activities are linked to the ability of the component macrocycles to mimic a β‐strand geometry that is known to favor active‐site binding. This ability is defined by conformational searches and docking studies with calpain.
Synthesis of Highly Functionalized Fluorinated Cispentacin Derivatives
Authors: Nonn Melinda , Kiss Loránd , Hänninen Mikko M. , Sillanpää Reijo , Fülöp Ferenc
Published: November 2012

Fluorinated highly functionalized cispentacin derivatives were synthetised starting from an unsaturated bicyclic β‐lactam through CC bond functionalization via the dipolar cycloaddition of a nitrile oxide, isoxazoline opening, and fluorination by OH/F exchange.
Hydrothermal Synthesis of Pencil‐like SAPO‐5 and Observation of Its Reversed Crystal‐Growth Process
Authors: Yang Qing , Li Ming , Zeng Changfeng , Zhang Lixiong
Published: November 2012

SAPO‐5 with a novel hexagonal pencil‐like morphology was hydrothermally synthesized from hydrogels that contain triethylamine and high concentrations of acetic acid at 180 °C for 48 h. The effect of the acetic acid concentration was examined and indicated that usage of a high concentration of acetic acid is crucial to the synthesis of SAPO‐5 with a pencil‐like morphology. The time‐dependent growth process of novel SAPO‐5 was observed by scanning electron microscopy with the aid of acid treatment to remove the amorphous materials for clearer observation. The samples were also characterized by X‐ray diffraction and Fourier‐transform infrared spectroscopy. The results show that the crystal growth at the early stage follows the reversed crystal‐growth route. First, the crystallization occurs on the surface of the aggregated amorphous ellipsoidal particles to form a hexagonal prism crystal shell with the encapsulation of amorphous materials. Then, the amorphous materials wrapped inside start to grow to a hexagonal prism inside the hollow larger hexagonal prism shell. Finally, the interior hexagonal prism continues to grow to the two ends with its length beyond that of the larger one by means of the Ostwald ripening process, thus forming the pencil‐like crystal.
ChemInform Abstract: Intermetallic Solid Solution Fe1‐xCoxGa3: Synthesis, Structure, NQR Study and Electronic Band Structure Calculations.
Authors: Shevelkov A. V. , et al. et al.
Published: November 2012

The title solid solutions with 0 ≤ x ≤ 1 are synthesized from the elements using excess Ga (1123 K, 55 h).
ChemInform Abstract: Synthesis, Structure, Physical Properties, and Electronic Structure of KGaSe2.
Authors: Feng Kai , Mei Dajiang , Bai Lei , Lin Zheshuai , Yao Jiyong , Wu Yicheng
Published: November 2012

High quality single crystals of the title compound are synthesized by solid state reaction of K2Se and Ga2Se3 (sealed silica tube, 800 °C, 72 h) and characterized by single crystal XRD, IR spectroscopy, diffuse reflectance spectroscopy, and DFT band structure calculations.
ChemInform Abstract: Structural Distortions in Sr3‐xAxMO4F (A: Ca, Ba; M: Al, Ga, In) anti‐Perovskites and Corresponding Changes in Photoluminescence.
Authors: Sullivan Eirin , Avdeev Maxim , Vogt Thomas
Published: November 2012

Sr2.975Ce0.025AlO4F, Sr2.95Ce0.025Na0.025AlO4F, and Sr2.25Ba0.6Eu0.1M0.95 In0.05O4‐αF1‐δ (M: Al, Ga) are characterized by neutron powder diffraction.
ChemInform Abstract: Full Differentiation and Assignment of Boron Species in the Electrolytes Li2B6O9F2 and Li2B3O4F3 by Solid‐State 11B NMR Spectroscopy.
Authors: Braeuniger Thomas , Pilz Thomas , Chandran C. Vinod , Jansen Martin
Published: November 2012

The title compounds, which possess considerable ion conductivity at higher temperatures, are characterized by solid state 11B MAS NMR spectroscopy.
ChemInform Abstract: Robust Acenaphthoimidazolylidene Palladium Complexes: Highly Efficient Catalysts for Suzuki—Miyaura Couplings with Sterically Hindered Substrates.
Authors: Tu Tao , Sun Zheming , Fang Weiwei , Xu Mizhi , Zhou Yunfei
Published: November 2012

At low catalyst loading, aryl bromides or aryl chlorides undergo the title coupling reaction to give di‐, tri‐ and tetra‐ortho‐substituted biaryls in excellent yields, including functionalized biaryls.
ChemInform Abstract: Highly Enantioselective Electrophilic α‐Bromination of Enecarbamates: Chiral Phosphoric Acid and Calcium Phosphate Salt Catalysts.
Authors: Alix Aurelien , Lalli Claudia , Retailleau Pascal , Masson Geraldine
Published: November 2012

The stereochemical reversal observed by changing the catalyst from chiral phosphoric acid to its calcium salt, is explained by different transition state models.
ChemInform Abstract: Selective “One‐Pot” Synthesis of Functionalized Cyclopentenones.
Authors: Varea Teresa , Alcalde Ana , Lopez de Dicastillo Carolina , Ramirez de Arellano Carmen , Cossio Fernando P. , Asensio Gregorio
Published: November 2012

Reaction of squaric acid derivatives with vinyl magnesium bromide followed by treatment with trifluoroethanol allows a new and stereoselective access to functionalized cyclopentenones of type (III)/ (V).
ChemInform Abstract: A Practical and General Diels—Alder Reaction of Pentafulvenes with Arynes.
Authors: Bhojgude Sachin Suresh , Kaicharla Trinadh , Bhunia Anup , Biju Akkattu T.
Published: November 2012

Using an optimized amount of CsF for the generation of the arynes from silylaryl triflates, a range of benzo‐fused norbornadiene derivatives is formed by cycloaddition with 6‐ or 6,6‐substituted pentafulvenes.
ChemInform Abstract: Synthesis of Alcohols via a Rhodium‐Catalyzed Hydroformylation—Reduction Sequence Using Tertiary Bidentate Amine Ligands.
Authors: Cheung Lawrence L. W. , Vasapollo Giuseppe , Alper Howard
Published: November 2012

Aromatic styrenes and related compounds give the desired alcohols with excellent chemoselectivity employing optimized conditions (solvent, reaction temperature, gas pressure, ligand).
ChemInform Abstract: Unusual Michael Reaction of 3‐(4‐Chlorophenyl)‐1‐phenylprop‐2‐en‐1‐one with 3‐Amino‐N‐phenyl‐3‐thioxopropanamide.
Authors: Dyachenko V. D. , Krasnikov D. A.
Published: November 2012

NaOH‐mediated reaction of chalcone (I) with thioxopropanamide (II) in EtOH does not yield the expected pyridinethione (V), but a Michael type adduct (III).
ChemInform Abstract: Palladium‐Catalyzed Cyanide Metathesis: Utilization of Benzyl Cyanide as an Operator‐Benign Reagent for Aryl Halide Cyanations.
Authors: Wen Qiaodong , Jin Jisong , Hu Binbin , Lu Ping , Wang Yanguang
Published: November 2012

Benzyl cyanide (II) is a safe and effective cyanation reagent for palladium‐catalyzed cyanation of haloarenes, affording the corresponding aryl nitriles in moderate to good yields.
ChemInform Abstract: Novel Synthetic Methodologies. Part 11. A Facile and Efficient Bi(III) Catalyzed Synthesis of 1,1‐Dihydroperoxides and 1,2,4,5‐Tetraoxanes.
Authors: Sashidhara Koneni V. , Avula Srinivasa Rao , Singh L. Ravithej , Palnati Gopala Reddy
Published: November 2012

A highly efficient synthesis of 1,1‐dihydroperoxides is achieved by Bi(III)‐catalyzed oxidation of aldehydes or ketones with hydrogen peroxide.
ChemInform Abstract: Highly Regioselective Synthesis of Aryl Chalcogenides Through C—H Functionalization of Arenes.
Authors: Cheng Jun‐Hao , Yi Chih‐Lun , Liu Tsung‐Jui , Lee Chin‐Fa
Published: November 2012

The regioselective synthesis of title compounds (III) and (V) through the Ir‐catalyzed meta C—H borylation followed by Cu‐catalyzed C—S coupling reaction with chalcogenide sources (II) and (IV) in one‐pot, giving the 3,5‐disubstituted aryl chalcogenides with high regioselectivity is reported.
ChemInform Abstract: Unexpected Formation of 4‐Arylcyclopentane‐1,1,3,3‐tetracarboxylates (II) in GaCl3‐Catalyzed Reaction of 2‐Arylcyclopropane‐1,1‐dicarboxylates (I) with Tetrasubstituted 1‐Pyrazolines.
Authors: Novikov Roman A. , Tomilov Yury V. , Nefedov Oleg M.
Published: November 2012

The Lewis acid‐catalyzed reaction of 2‐arylcyclopropane‐1,1‐dicarboxylates (I) in the presence of pyrazoline dicarboxylates (III) containing no hydrogen atoms in C‐3 or C‐5 positions of the heterocycle is presented.
ChemInform Abstract: Pd(0) NPs: A Novel and Reusable Catalyst for the Synthesis of Bis(heterocyclyl)methanes in Water.
Authors: Saha Mithu , Pal Amarta Kumar , Nandi Shibaji
Published: November 2012

Hydroxy coumarin (I), indole (IV), dimedone (VI), and pyrazole (VIII) react with various aromatic aldehydes (II) in the presence of in situ generated palladium nanoparticles giving the title compounds in high yields.
ChemInform Abstract: Stereoselective Double Lewis Acid/Organo‐Catalyzed Dimerization of Donor—Acceptor Cyclopropanes into Substituted 2‐Oxabicyclo[3.3.0]octanes.
Authors: Novikov Roman A. , Timofeev Vladimir P. , Tomilov Yury V.
Published: November 2012

In the presence of GaCl3 and the pyrazoline, cyclopropanes of type (I) undergo new and stereoselective dimerization to afford oxabicyclooctanes like (II).
ChemInform Abstract: Synthetic Approach Toward cis‐Disubstituted γ‐ and δ‐Lactones Through Enantioselective Dialkylzinc Addition to Aldehydes: Application to the Synthesis of Optically Active Flavors and Fragrances.
Authors: Pisani Laura , Superchi Stefano , D'Elia Alessandra , Scafato Patrizia , Rosini Carlo
Published: November 2012

The synthesis of the cis‐whisky lactone (VIIc) based on enantioselective catalysis is presented for the first time.
ChemInform Abstract: 1,3‐Dipolar Cycloaddition Reaction of 3‐Trifluoromethyl‐4‐diazopyrazolinones with Acetylenedicarboxylates.
Authors: Zhang Zhenhua , Wang Xiaowei , Tao Song , Zhu Shizheng
Published: November 2012

Two different methods for the preparation of the title compounds from the compounds (II) are successfully developed.
ChemInform Abstract: Synthesis of 1,2,4,5‐Tetrasubstituted Imidazoles Using Sulfuric Acid ([3‐(3‐Silicapropyl)sulfanyl]propyl)ester as a Recyclable Solid Acid.
Authors: Tavakoli Ziba , Bagherneghad Mojtaba , Niknam Khodabakhsh
Published: November 2012

The title acid catalyzes the four‐component condensation of benzil (I), aliphatic and aromatic amines (II), aromatic aldehydes (III), and ammonium acetate under solvent‐free conditions, possibly by increasing the electrophilicity of the carbonyl group of (I) and (III).
ChemInform Abstract: Synthesis of a New Class of Arylsulfonylethylsulfonylmethyloxazolines and Thiazolines.
Authors: Padmavathi Venkatapuram , Venkatesh Bhumireddy C. , Premakumari Chokkappagari , Padmaja Adivireddy
Published: November 2012

The entitled compounds (III) are formed using a multistep one‐pot methodology exploiting either lanthanide catalysis or microwave irradiation in a single step with high yields.
ChemInform Abstract: Facile One‐Pot Procedure for the Synthesis of 2‐Aminothiazole Derivatives.
Authors: Yin Guodong , Ma Junrui , Shi Houqiang , Tao Qing
Published: November 2012

α‐Bromination of aromatic methyl ketones (I) followed by cyclization with thiourea derivatives (II) affords aminothiazole derivatives (III) in moderate to good yields.
ChemInform Abstract: Multi‐Component Synthesis of 2‐Amino‐6‐(alkylthio)pyridine‐3,5‐dicarbonitriles Using Zn(II) and Cd(II) Metal—Organic Frameworks (MOFs) under Solvent‐Free Conditions.
Authors: Thimmaiah Muralidhara , Li Peng , Regati Sridhar , Chen Banglin , Zhao John Cong‐Gui
Published: November 2012

Both MOF′s (I) reveal analogous efficiency concerning reaction time and yield.
ChemInform Abstract: Ring Expansion of Cyclic β‐Amino Alcohols Induced by Diethylaminosulfur Trifluoride: Synthesis of Cyclic Amines with a Tertiary Fluorine at C‐3.
Authors: Anxionnat Bruno , Robert Benoit , George Pascal , Ricci Gino , Perrin Marc‐Antoine , Gomez Pardo Domingo , Cossy Janine
Published: November 2012

The ring expansion of 2‐hydroxymethyl azetidines and prolinols proceeds with high enantioselectivity for small rings.
ChemInform Abstract: A New and Facile Access to the 2‐(Indol‐3‐yl)‐3‐nitriloquinolines Based on Friedlaender Annulations.
Authors: Shiri Morteza , Zolfigol Mohammad Ali , Pirveysian Mahtab , Ayazi‐Nasrabadi Roya , Kruger Hendrik G. , Naicker Tricia , Mohammadpoor‐Baltork Iraj
Published: November 2012

A multi‐step one‐pot procedure for the synthesis of the title compounds is reported in relative short reaction times.
ChemInform Abstract: An Efficient Method for the Synthesis of 4‐Arylfuro[2,3‐a][4,7]phenanthroline Derivatives Catalyzed by Iodine.
Authors: Wang Xiang‐Shan , Yin Ming‐Yue , Wang Shu‐Liang , Wang Wei , Li Yu‐Ling
Published: November 2012

The title compounds (IV) are efficiently obtained in a three‐component one‐pot reaction of various aromatic aldehydes (13 examples) with quinilin‐6‐amine (I) and 2,3‐dihydrofuran (III) under mild reaction conditions.
ChemInform Abstract: Benzo[b]furan in the Povarov Reaction.
Authors: Krainova Gulnaz F. , Chudinova Yulia O. , Gorbunov Alexey A. , Mayorova Olga A. , Glushkov Vladimir A.
Published: November 2012

Povarov‐type condensation of benzofuran with Schiff bases provides access to benzofuroquinoline derivatives.
ChemInform Abstract: Bis(α‐bromo ketones): Versatile Precursors for Novel Bis(s‐triazolo[3,4‐b][1,3,4]thiadiazines) and Bis(as‐triazino[3,4‐b][1,3,4]thiadiazines).
Authors: Shaaban Mohamed R. , Elwahy Ahmed H. M.
Published: November 2012

Cyclization of bis(α‐bromoketones) (II) and (VII) with aminotriazoles (III) and aminotriazine (VIII), resp., provides access towards title fused thiadiazines (IV) and (IX), resp., in moderate yields.
ChemInform Abstract: Copper(I)‐Catalyzed Cascade Sulfonimidate to Sulfonamide Rearrangement: Synthesis of Imidazo[1,2‐a][1,4]diazepin‐7(6H)‐one.
Authors: Nagaraj Muthupandi , Boominathan Muthusamy , Perumal Devanathan , Muthusubramanian Shanmugam , Bhuvanesh Nattamai
Published: November 2012

Cu‐mediated treatment of alkynols of type (I) with sulfonyl azides results in formation of ketenimines which spontaneously undergo cyclization to sulfonimidates and rearrangement to sulfonamides.
ChemInform Abstract: Copper(I)‐Catalyzed Regio‐ and Chemoselective Single and Double Addition of Nucleophilic Silicon to Propargylic Chlorides and Phosphates.
Authors: Hazra Chinmoy K. , Oestreich Martin
Published: November 2012

Treatment of linear propargylic chlorides and phosphates with equimolar amounts of Zn agents (II) and (IX) allows an efficient and regioselective formation of silylated allenes.
ChemInform Abstract: Asymmetric Synthesis of (—)‐(R)‐Massoia Lactone (V), (R)‐δ‐Decalactone (VI), and (+)‐(3R,5R)‐3‐Hydroxydecano‐5‐lactone (IX). Formal Synthesis of Verbalactone (X).
Authors: Mineeva I. V.
Published: November 2012

involving asymmetric allylation of hexanal with stannane (II) as the key step
ChemInform Abstract: Nonstoichiometry in Inorganic Fluorides: Part 1. Nonstoichiometry in MFm—RFn (m < n ≤ 4) Systems
Authors: Sobolev B. P.
Published: November 2012

Review: synthesis, phase diagrams, and crystal growth in title systems with M: alkali etals, alkaline earth metals, transition metals and R: lanthanoids; 66 refs.
ChemInform Abstract: Highly Frustrated Magnetism in Spinels
Authors: Takagi Hidenori , Niitaka Seiji
Published: November 2012

Review: 97 refs.
ChemInform Abstract: Luminescent Ionic Transition Metal Complexes for Light‐Emitting Electrochemical Cells
Authors: Costa Ruben D. , Orti Enrique , Bolink Henk J. , Monti Filippo , Accorsi Gianluca , Armaroli Nicola
Published: November 2012

Review: 211 refs.
ChemInform Abstract: How to Control the Selectivity of Palladium‐Based Catalysts in Hydrogenation Reactions: The Role of Subsurface Chemistry.
Authors: Behrens Malte , et al. et al.
Published: November 2012

Review: 80 refs.
ChemInform Abstract: Synthesis of Extended Porphyrins by Connection of meso‐Aryl Groups with β‐Pyrrolic Positions
Authors: Pereira Ana M. V. M. , Richeter Sebastien , Jeandon Christophe , Gisselbrecht Jean‐Paul , Wytko Jennifer , Ruppert Romain
Published: November 2012

Review: 91 refs.
ChemInform Abstract: Radical‐Mediated Dimerization and Oxidation Reactions for the Synthesis of Complex Alkaloids
Authors: Lathrop Stephen P. , Kim Justin , Movassaghi Mohammad
Published: November 2012

Review: 52 refs.
ChemInform Abstract: Heterocyclic Chemistry
Authors: Aldabbagh Fawaz
Published: November 2012

Review: 82 refs.
ChemInform Abstract: Highlight Syntheses
Authors: Downer‐Riley Nadale K. , Jackson Yvette A.
Published: November 2012

Review: 29 refs.
ChemInform Abstract: Electric Field Control of Magnetism in Multiferroic Heterostructures
Authors: Vaz C. A. F.
Published: November 2012

Review: 632 refs.
ChemInform Abstract: Gas Phase Basicities of Polyfunctional Molecules. Part 3. Amino Acids
Authors: Bouchoux Guy
Published: November 2012

Review: 217 refs.
Synthesis of Transition‐Metal Exchanged Nanocrystalline ZSM‐5 and Their Application in Electrochemical Oxidation of Glucose and Methanol
Authors: Kaur Balwinder , Anu Prathap M. U. , Srivastava Rajendra
Published: November 2012

Nanocrystalline ZSM‐5 was prepared using propyltriethoxysilane. Materials were characterized by a complementary combination of X‐ray diffraction, nitrogen sorption, and scanning electron microscopy. Transition‐metal ion exchanged nanocrystalline ZSM‐5‐modified electrodes were constructed for the electrocatalytic oxidation of glucose and methanol. A non‐enzymatic electrochemical sensor based on a Ni2+‐exchanged nanocrystalline ZSM‐5‐modified electrode exhibits the highest sensing ability, whereas the corresponding Cu2+‐exchanged electrode exhibits the highest current sensitivity for glucose oxidation. Among the variety of electrodes modified with transition‐metal ion exchanged nanocrystalline ZSM‐5, the Ni2+‐exchanged electrode exhibits high current sensitivity and sensing ability in methanol oxidation. Electrocatalytic activity of conventional ZSM‐5‐modified electrodes was significantly low compared to nanocrystalline ZSM‐5‐modified electrodes. Enhancement in the electrocatalytic activities of nanocrystalline ZSM‐5‐modified electrodes can be correlated with the enhanced accessibility of glucose/methanol to M2+ active centers in the nanocrystalline ZSM‐5 owing to its large specific surface area and intercrystalline mesopores. The sensor was applied directly to determine glucose concentration in adult human blood serum, and the precision of the method was found to be satisfactory. The non‐enzymatic sensor exhibited excellent reproducibility, repeatability, stability, and antifouling ability for direct determination of glucose in human blood serum.
Serial anthropometry predicts peripheral nerve dysfunction in a community cohort
Authors: Ylitalo Kelly R. , Herman William H. , Harlow Siobán D.
Published: November 2012

Background

Obesity is a risk factor for glucose intolerance, but the independent role of obesity in the development of peripheral neuropathy is unclear. This study assessed the impact of body size trajectories on prevalent nerve dysfunction in community‐dwelling women with and without glucose intolerance.

Methods

Annual (1996–2008) anthropometric measures of weight, height, waist circumference and body mass index [BMI, weight (kg)/height (m2)] were assessed in the Study of Women's Health Across the Nation – Michigan site. Glucose intolerance was defined annually on the basis of current use of diabetes medications, self‐reported diabetes diagnosis and, when available, fasting glucose. Peripheral nerve dysfunction in 2008 was defined as abnormal monofilament testing or ≥4 symptoms or signs. Linear mixed models were used to determine trajectories of anthropometry by subsequently identified nerve dysfunction status.

Results

Mean BMI was 32.4 kg/m2 at baseline, and 27.8% of the women had nerve dysfunction in 2008. BMI, weight and waist circumference increased over time. Women who would have nerve dysfunction were significantly larger than women without dysfunction, independent of glucose intolerance. At mean baseline age of 46, BMI, weight and waist circumference differed significantly (p‐value < 0.01) by subsequent nerve dysfunction status, independent of glucose intolerance and hypertension. These body size differences were maintained but not exacerbated over time.

Conclusions

Peripheral nerve dysfunction is prevalent among community‐dwelling women. Twelve years before the nerve assessment, anthropometry differed between women who would and would not have nerve dysfunction, differences that were maintained over time. Obesity deserves attention as an important and potentially modifiable risk factor for peripheral nerve dysfunction. Copyright © 2012 John Wiley & Sons, Ltd.
Notch1 modulates mesenchymal stem cells mediated regulatory T‐cell induction
Authors: Del Papa Beatrice , Sportoletti Paolo , Cecchini Debora , Rosati Emanuela , Balucani Chiara , Baldoni Stefano , Fettucciari Katia , Marconi Pierfrancesco , Martelli Massimo F. , Falzetti Franca , Di Ianni Mauro
Published: November 2012

Notch1 signaling is involved in regulatory T (Treg)‐cell differentiation. We previously demonstrated that, when cocultured with CD3+ cells, mesenchymal stem cells (MSCs) induced a T‐cell population with a regulatory phenotype. Here, we investigated the molecular mechanism underlying MSC induction of human Treg cells. We show that the Notch1 pathway is activated in CD4+ T cells cocultured with MSCs. Inhibition of Notch1 signaling through GSI‐I or the Notch1 neutralizing antibody reduced expression of HES1 (the Notch1 downstream target) and the percentage of MSC‐induced CD4+CD25highFOXP3+ cells in vitro. Moreover, we demonstrate that FOXP3 is a downstream target of Notch signaling in human cells. No crosstalk between Notch1 and TGF‐β signaling pathways was observed in our experimental system. Together, these findings indicate that activation of the Notch1 pathway is a novel mechanism in the human Treg‐cell induction mediated by MSCs.
HCV‐infected hepatocytes drive CD4+CD25+Foxp3+ regulatory T‐cell development through the Tim‐3/Gal‐9 pathway
Authors: Ji Xiao J. , Ma Cheng J. , Wang Jia M. , Wu Xiao Y. , Niki Toshiro , Hirashima Mitsumi , Moorman Jonathan P. , Yao Zhi Q.
Published: November 2012

HCV is remarkable at disrupting human immunity to establish chronic infection. The accumulation of Treg cells at the site of infection and upregulation of inhibitory signaling pathways (such as T‐cell Ig and mucin domain protein‐3 (Tim‐3) and galectin‐9 (Gal‐9)) play pivotal roles in suppressing antiviral effector T (Teff) cells that are essential for viral clearance. While Tim‐3/Gal‐9 interactions have been shown to negatively regulate Teff cells, their role in regulating Treg cells is poorly understood. To explore how Tim‐3/Gal‐9 interactions regulate HCV‐mediated Treg‐cell development, here we provide pilot data showing that HCV‐infected human hepatocytes express higher levels of Gal‐9 and TGF‐β, and upregulate Tim‐3 expression and regulatory cytokines TGF‐β/IL‐10 in co‐cultured human CD4+ T cells, driving conventional CD4+ T cells into CD25+Foxp3+ Treg cells. Additionally, recombinant Gal‐9 protein can transform TCR‐activated CD4+ T cells into Foxp3+ Treg cells in a dose‐dependent manner. Importantly, blocking Tim‐3/Gal‐9 ligations abrogates HCV‐mediated Treg‐cell induction by HCV‐infected hepatocytes, suggesting that Tim‐3/Gal‐9 interactions may regulate human Foxp3+ Treg‐cell development and function during HCV infection.
The influence of the type of oil phase on the self‐assembly process of γ‐oryzanol + β‐sitosterol tubules in organogel systems
Authors: Sawalha Hassan , Margry Giel , den Adel Ruud , Venema Paul , Bot Arjen , Flöter Eckhard , van der Linden Erik
Published: November 2012

Mixtures of γ‐oryzanol and β‐sitosterol were used to structure different oils (decane, limonene, sunflower oil, castor oil, and eugenol). The γ‐oryzanol and β‐sitosterol mixtures self‐assemble into double‐walled hollow tubules (∼10 nm in diameter) in the oil phase, which aggregate to form a network resulting in firm organogels. The self‐assembly of the sterol molecules into tubules was studied using light scattering and rheology. By using different oils, the influence of the polarity of the oil on the self‐assembly was studied. The effects of temperature and structurant concentration on the tubuler formation process were determined and the thermodynamic theory of self‐assembly was applied to calculate the change in Gibbs free energy (ΔG0), enthalpy (ΔH0), and entropy (ΔS0) resulting from the aggregation of the structurants was determined. The self‐assembly was found to be enthalpy‐driven as characterized by a negative ΔH0 and ΔS0. A decreasing polarity of the oil promotes the self‐assembly leading to formation of tubules at higher temperatures and lower structurant concentrations.
Detection of adulteration of sesame and peanut oils via volatiles by GC × GC–TOF/MS coupled with principal components analysis and cluster analysis
Authors: Zhao Fangfang , Liu Jingkun , Wang Xiupin , Li Peiwu , Zhang Wen , Zhang Qi
Published: November 2012

The method of headspace coupled with comprehensive two‐dimensional GC–time‐of‐flight MS (HS‐GC × GC–TOF/MS) was applied to differentiate the volatile flavor compounds of three types of pure vegetable oils (sesame oils, peanut oils, and soybean oils) and two types of adulterated oils (sesame oils and peanut oils adulterated with soybean oils). Thirty common volatiles, 14 particular flavors and two particular flavors were identified from the three types of pure oils, from the sesame oils, and from the soybean oils, respectively. Thirty‐one potential markers (variables), which are crucial to the forming of different vegetable oil flavors, were selected from volatiles in different pure and adulterated oils, and they were analyzed using the principal component analysis (PCA) and cluster analysis (CA) approaches. The samples of three types of pure vegetable oil were completely classified using the PCA and CA. In addition, minimum adulteration levels of 5 and 10% can be differentiated in the adulteration of peanut oils and sesame oils with soybean oils, respectively.

Practical applications: The objective was to develop one kind of potential differentiated method to distinguish high cost vegetable oils from lower grade and cheaper oils of poorer quality such as soybean oils. The test result in this article is satisfactory in discriminating adulterated oils from pure vegetable oils, and the test method is proved to be effective in analyzing different compounds. Furthermore, the method can also be used to detect other adulterants such as hazelnut oil and rapeseed oil. The method is an important technical support for public health against profit‐driven illegal activities.
Manganese(III) acetate induced radical addition of azide to unsaturated fatty compounds
Authors: Biermann Ursula , Linker Ursula , Metzger Jürgen O.
Published: November 2012

Nitrogen functionalities can be introduced in the alkyl chain of unsaturated fatty compounds by addition of azide mediated by manganese(III) acetate. The respective reaction of methyl oleate 1 containing an internal C,C double bond gave allyl azide 3 as a mixture of 4 regioisomers while the addition of azide to the terminal C,C double bond of methyl 10‐undecenoate 2 afforded the vicinal diazide 6. Azide 3 could be easily converted to the saturated amine 4 by catalytic hydrogenation and to the allyl amines 5 by the Staudinger reaction.