bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis, characterization, and thermo mechanical properties of siloxane‐modified epoxy‐based nano composite
Authors: Chiu Yie‐Chan , Huang Chun‐Chiang , Tsai Hsieh‐Chih
Published: June 2014

In this study, polymer hybrid composites were synthesized by sol‐gel process. 3‐Amino‐propyltrimethoxysilane [APTMS)/γ‐Glycidoxypropyl trimethoxy‐silane (GPTMS); (4, 4′‐Methylene‐dianiline (DDM)] and 1,4‐Bis(trimethoxysilylethyl) benzene (BTB) were added to DGEBA type epoxy resin for anticipated to exhibit excellent thermal stability. Boron trifluoride monoethylamine (BF3MEA) was used as catalyst. The structure of nanocomposites was characterized by attenuated total reflectance (ATR) and solid‐state 29Si NMR which suggest EP‐APTMS‐BTB/EP‐GPTMS‐BTB possesses T3; T1–T0, and T1 structures when the BTB content was lower than 10 wt % and higher 20 wt %, respectively. BF3MEA was proved to be an effective catalyst for the sol‐gel reaction of APTMS, but it could not promote for GPTMS. From TEM microphotographs, EP‐APTMS‐BTB (10 wt %) possesses a dense inorganic structure (particle size around 5–15 nm) compare with the loose inorganic structure of EP‐GPTM‐/BTB (10 wt %). DSC, TGA were use to analyze the thermal properties of the nanocomposites and DMA was used to analyze the dynamic mechanical properties of hybrid composites. The Tgs of all nanocomposites decreased with the increasing BTB content. A system with BTB content lower than 10 wt % showed good dynamic mechanical property and thermal stability (Td5 increased from 336°C to 371°C, char yield increased from 27.4 to 30.2%). The structure of inorganic network affects the Td5 and dynamic mechanical properties of composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40984.
Calcium‐dependent cysteine proteinase (calpain) in human arthritic synovial joints
Authors: Yamamoto Shingo , Shimizu Katsuji , Shimizu Kazuya , Suzuki Kiichi , Nakagawa Yasuaki , Yamamuro Takao
Published: June 2014

Objective. To study the roles of calpains in the synovial joint in rheumatoid arthritis (RA) and osteoarthritis (OA) and to verify the hypothesis that calpains present in the synovial fluid come from the synovium.

Methods. We performed immunohistochemical, biochemical, and immunoblotting analyses for calpains in synovial tissues, synovial cell cultures, and synovial fluids.

Results. Immunohistochemical staining of RA synovium demonstrated specific cytoplasmic staining of cells in the synovial lining layer, storomal fibroblasts, and endothelial cells. OA synovium showed almost the same intensity and distribution of calpain staining. DEAE‐cellulose chromatography of RA and OA synovial extracts and synovial fluids showed a peak of caseinolytic activity attributable to calpain, as well as an inhibitory peak of calpastatin, a specific inhibitor protein of calpains. Immunoblotting using the anticalpain antibody from the calpain peak of RA and OA synovium and synovial fluid showed identity with the heavy subunit of calpain (80 kd). Similarly, calpain existed in the same form (80 kd) in conditioned media (supernatant) obtained from synovial cell cultures, as well as in the synoviocytes. The total specific activity of the 2 calpains in the synovial fluid of RA patients was higher than that of calpastatin.

Conclusion. The findings suggest that the extracellular appearance of calpains could be due to the secretion of these proteins from the synovial cells and that calpains may play a role in cartilage damage of RA and OA that occurs in synovial joints.
Efficacy and safety of 10‐deazaaminopterin in the treatment of rheumatoid arthritis: A one‐year continuation, double‐blind study
Authors: Alarcón Graciela S. , Castañeda Oswaldo , Ferrándiz Manuel , Krumdieck Carlos L. , Koopman William J.
Published: June 2014

Objective. To determine the long‐term safety and efficacy of 10‐deazaaminopterin (10‐DAM) in the treatment of rheumatoid arthritis (RA).

Methods. A 1‐year continuation of an initial 15‐week randomized, double‐blind clinical trial of 10‐DAM and methotrexate (MTX).

Results. 10‐DAM (n = 10) and MTX (n = 8) had comparable safety and efficacy profiles. One 10‐DAM—treated and 2 MTX‐treated patients experienced transient side effects; 1 MTX‐treated patient experienced recurrent nausea and discontinued MTX.

Conclusion. 10‐DAM appears to be as beneficial and as safe as MTX for the treatment of RA.
The treatment of wegener's granulomatosis with glucocorticoids and methotrexate
Authors: Hoffman Gary S. , Leavitt Randi Y. , Kerr Gail S. , Fauci Anthony S.
Published: June 2014

Objective. To identify alternatives to daily low‐dose cyclophosphamide (CYC) in the treatment of Wegener's granulomatosis (WG).

Methods. An open‐label pilot study of weekly low‐dose methotrexate (MTX) plus glucocorticoids (GC) for treatment of patients with WG was performed. Twenty‐nine patients who did not have immediately life‐threatening disease were included. Outcome was determined by clinical characteristics, pathologic findings, course of illness, laboratory and radiographic findings, and successful withdrawal of GC therapy.

Results. Weekly administration of MTX (at a mean stable dosage of 20 mg) and GC resulted in marked improvement in 76% of the 29 patients. Remission was achieved in 69% of the patients, 7% improved but had intermittent smoldering disease that precluded total withdrawal of GC, and 17% had progressive disease within 2–6 months of starting the study treatment. Two patients who initially achieved remission later had relapses after GC was discontinued. Of those who remain in remission (mean followup time 14.5 months), 72% have not required GC for a mean period of 10 months.

Conclusion. Although standard therapy for WG (daily CYC and GC) has dramatically improved outcome in this often‐fatal disease, treatment morbidity has led to attempts to identify effective interventions that have less toxicity. Weekly low‐dose MTX was shown in this study to be a feasible alternative to CYC in patients whose illness was not immediately life‐threatening or in whom prior CYC treatment was ineffective or produced serious toxicity. Although these results are preliminary, they are encouraging and justify further studies in which MTX, CYC, and other alternative therapeutic approaches are compared concurrently.
Serum anti—SS‐B/La and IgA rheumatoid factor are markers of salivary gland disease activity in primary sjögren's syndrome
Authors: Atkinson Jane C. , Travis William D. , Slocum Linda , Ebbs William L. , Fox Philip C.
Published: June 2014

Objective. To identify serologic markers of salivary gland disease activity in 43 patients with primary Sjögren's syndrome.

Methods. Comparison of salivary gland biopsies (focus scores) and flow rates with serum concentrations of IgA and IgM rheumatoid factor (RF), total serum IgG, serum anti—SS‐B/La antibodies, and the erythrocyte sedimentation rate.

Results. Serum anti—SS‐B/La antibody levels correlated with focus scores (rs = 0.477, P < 0.0025). Serum IgA‐RF concentrations correlated inversely with stimulated parotid gland salivary flow rates (rs = −0.394, P < 0.01).

Conclusion. Measuring serum levels of anti—SS‐B/La and IgA‐RF would be useful when monitoring salivary responses in therapeutic trials, especially in patients with minimal salivary function.
The phrase “information storage and retrieval” (IS&R): An historical note
Authors: Hjørland Birger
Published: June 2014

Scholars have uncovered abundant data about the history of the term “information,” as well as some of its many combined phrases (e.g., “information science,” “information retrieval,” and “information technology”). Many other compounds that involve “information” seem, however, not to have a known origin yet. In this article, further information about the phrase “information storage and retrieval” is provided. Knowing the history of terms and their associated concepts is an important prescription against poor terminological phrasing and theoretical confusion.
Citation‐based plagiarism detection: Practicability on a large‐scale scientific corpus
Authors: Gipp Bela , Meuschke Norman , Breitinger Corinna
Published: June 2014

The automated detection of plagiarism is an information retrieval task of increasing importance as the volume of readily accessible information on the web expands. A major shortcoming of current automated plagiarism detection approaches is their dependence on high character‐based similarity. As a result, heavily disguised plagiarism forms, such as paraphrases, translated plagiarism, or structural and idea plagiarism, remain undetected. A recently proposed language‐independent approach to plagiarism detection, Citation‐based Plagiarism Detection (CbPD), allows the detection of semantic similarity even in the absence of text overlap by analyzing the citation placement in a document's full text to determine similarity. This article evaluates the performance of CbPD in detecting plagiarism with various degrees of disguise in a collection of 185,000 biomedical articles. We benchmark CbPD against two character‐based detection approaches using a ground truth approximated in a user study. Our evaluation shows that the citation‐based approach achieves superior ranking performance for heavily disguised plagiarism forms. Additionally, we demonstrate CbPD to be computationally more efficient than character‐based approaches. Finally, upon combining the citation‐based with the traditional character‐based document similarity visualization methods in a hybrid detection prototype, we observe a reduction in the required user effort for document verification.
Visible‐Light Photocatalytic Hydrogen Production Activity of ZnIn2S4 Microspheres Using Carbon Quantum Dots and Platinum as Dual Co‐catalysts
Authors: Li Qin , Cui Can , Meng Huan , Yu Jiaguo
Published: June 2014

ZnIn2S4 microspheres (ZIS MSs) were for the first time decorated with carbon quantum dots (CQDs) and platinum nanoparticles (NPs) as dual co‐catalysts of for photocatalytic H2 production. The ZIS MSs co‐loaded with CQDs and Pt exhibited a high photocatalytic H2 production rate of 1032.2 μmol h−1 g−1 with an apparent quantum efficiency of 2.2 % (420 nm) in triethanolamine aqueous solution under visible‐light irradiation, which was much higher than the respective photocatalytic rates of pure ZIS, Pt loaded ZIS, and CQDs‐decorated ZIS. Such a great enhancement was attributed to the integrative effect of good crystallization, enhanced light absorption, high electrical conductivity of CQDs, and the vectorial electron transfer from ZIS to CQDs and Pt NPs (ZIS→CQDs→Pt).
Group‐effort applied research: Expanding opportunities for undergraduate research through original, class‐based research projects
Authors: Moore Sean D. , Teter Ken
Published: June 2014

Undergraduate research clearly enriches the educational development of participating students, but these experiences are limited by the inherent inefficiency of the standard one student‐one mentor model for undergraduate research. Group‐effort applied research (GEAR) was developed as a strategy to provide substantial numbers of undergraduates with meaningful research experiences. The GEAR curriculum delivers concept‐driven lecture material and provides hands‐on training in the context of an active research project from the instructor's laboratory. Because GEAR is structured as a class, participating students benefit from intensive, supervised research training that involves a built‐in network of peer support and abundant contact with faculty mentors. The class format also ensures a relatively standardized and consistent research experience. Furthermore, meaningful progress toward a research objective can be achieved more readily with GEAR than with the traditional one student‐one mentor model of undergraduate research because sporadic mistakes by individuals in the class are overshadowed by the successes of the group as a whole. Three separate GEAR classes involving three distinct research projects have been offered to date. In this article, we provide an overview of the GEAR format and review some of the recurring themes for GEAR instruction. We propose GEAR can serve as a template to expand student opportunities for life science research without sacrificing the quality of the mentored research experience. © 2014 by The International Union of Biochemistry and Molecular Biology, 42(4):331–338, 2014.
Using analogy role‐play activity in an undergraduate biology classroom to show central dogma revision
Authors: Takemura Masaharu , Kurabayashi Mario
Published: June 2014

For the study of biology in an undergraduate classroom, a classroom exercise was developed: an analogy role‐play to learn mechanisms of gene transcription and protein translation (central dogma). To develop the central dogma role‐play exercise, we made DNA and mRNA using paper sheets, tRNA using a wire dress hanger, and amino acids using Lego® blocks (Lego System A/S, Denmark). Students were studying in the course of mathematics, physics, or chemistry, so biology was not among their usual studies. In this exercise, students perform the central dogma role‐play and respectively act out nuclear matrix proteins, a transcription factor, an RNA polymerase II, an mRNA transport protein, nuclear pore proteins, a large ribosomal subunit, a small ribosomal subunit, and several amino‐acyl tRNA synthetases. Questionnaire results obtained after the activity show that this central dogma role‐play analogy holds student interest in the practical molecular biological processes of transcription and translation. © 2014 by The International Union of Biochemistry and Molecular Biology, 42(4):351–356, 2014.
The impact of dietary isoflavonoids on malignant brain tumors
Authors: Sehm Tina , Fan Zheng , Weiss Ruth , Schwarz Marc , Engelhorn Tobias , Hore Nirjhar , Doerfler Arnd , Buchfelder Michael , Eyüpoglu IIker Y. , Savaskan Nic E.
Published: June 2014

Poor prognosis and limited therapeutic options render malignant brain tumors one of the most devastating diseases in clinical medicine. Current treatment strategies attempt to expand the therapeutic repertoire through the use of multimodal treatment regimens. It is here that dietary fibers have been recently recognized as a supportive natural therapy in augmenting the body's response to tumor growth. Here, we investigated the impact of isoflavonoids on primary brain tumor cells. First, we treated glioma cell lines and primary astrocytes with various isoflavonoids and phytoestrogens. Cell viability in a dose‐dependent manner was measured for biochanin A (BCA), genistein (GST), and secoisolariciresinol diglucoside (SDG). Dose–response action for the different isoflavonoids showed that BCA is highly effective on glioma cells and nontoxic for normal differentiated brain tissues. We further investigated BCA in ex vivo and in vivo experimentations. Organotypic brain slice cultures were performed and treated with BCA. For in vivo experiments, BCA was intraperitoneal injected in tumor‐implanted Fisher rats. Tumor size and edema were measured and quantified by magnetic resonance imaging (MRI) scans. In vascular organotypic glioma brain slice cultures (VOGIM) we found that BCA operates antiangiogenic and neuroprotective. In vivo MRI scans demonstrated that administered BCA as a monotherapy was effective in reducing significantly tumor‐induced brain edema and showed a trend for prolonged survival. Our results revealed that dietary isoflavonoids, in particular BCA, execute toxicity toward glioma cells, antiangiogenic, and coevally neuroprotective properties, and therefore augment the range of state‐of‐the‐art multimodal treatment approach.
Identification of a Novel Inhibition Site in Translocase MraY Based upon the Site of Interaction with Lysis Protein E from Bacteriophage ϕX174
Authors: Rodolis Maria T. , Mihalyi Agnes , O'Reilly Amy , Slikas Justinas , Roper David I. , Hancock Robert E. W. , Bugg Timothy D. H.
Published: June 2014

Translocase MraY is the site of action of lysis protein E from bacteriophage ϕX174. Previous genetic studies have shown that mutation F288L in transmembrane helix 9 of E. coli MraY confers resistance to protein E. Construction of a helical wheel model for transmembrane helix 9 of MraY and the transmembrane domain of protein E enabled the identification of an Arg‐Trp‐x‐x‐Trp (RWxxW) motif in protein E that might interact with Phe288 of MraY and the neighbouring Glu287. This motif is also found in a number of cationic antimicrobial peptide sequences. Synthetic dipeptides and pentapeptides based on the RWxxW consensus sequence showed inhibition of particulate E. coli MraY activity (IC50 200–600 μM), and demonstrated antimicrobial activity against E. coli (MIC 31–125 μg mL−1). Cationic antimicrobial peptides at a concentration of 100 μg mL−1 containing Arg‐Trp sequences also showed 30–60 % inhibition of E. coli MraY activity. Assay of the synthetic peptide inhibitors against recombinant MraY enzymes from Bacillus subtilis, Pseudomonas aeruginosa, and Micrococcus flavus (all of which lack Phe288) showed reduced levels of enzyme inhibition, and assay against recombinant E. coli MraY F288L and an E287A mutant demonstrated either reduced or no detectable enzyme inhibition, thus indicating that these peptides interact at this site. The MIC of Arg‐Trp‐octyl ester against E. coli was increased eightfold by overexpression of mraY, and was further increased by overexpression of the mraY mutant F288L, also consistent with inhibition at the RWxxW site. As this site is on the exterior face of the cytoplasmic membrane, it constitutes a potential new site for antimicrobial action, and provides a new cellular target for cationic antimicrobial peptides.
Molecular characteristics of residual cancer and stromal cells after chemoradiotherapy for gastric cancer: report of four cases
Authors: Tanaka Koji , Mohri Yasuhiko , Koike Yuhki , Okugawa Yoshinaga , Toiyama Yuji , Ohi Masaki , Kobayashi Minako , Inoue Yasuhiro , Araki Toshimitsu , Uchida Keiichi , Miki Chikao , Kusunoki Masato
Published: June 2014

Key Clinical Message

Four patients with gastric cancer underwent 5‐fluorouracil and cisplatin‐based chemoradiotherapy followed by surgery. Expression analysis of chemoradiosensitivity related genes in residual cancer using formalin‐fixed paraffin‐embedded specimens may be useful when determining a chemotherapy regimen for disease recurrence after chemoradiotherapy for gastric cancer.
Fischer–Tropsch Synthesis: Morphology, Phase Transformation, and Carbon‐Layer Growth of Iron‐Based Catalysts
Authors: Pendyala Venkat Ramana Rao , Graham Uschi M. , Jacobs Gary , Hamdeh Hussein H. , Davis Burtron H.
Published: June 2014

The morphological, phase transformations and carbon‐layer growth for unpromoted and K‐promoted iron catalysts were investigated over time during Fischer–Tropsch synthesis. Catalysts were activated in CO for 24 h, which transformed hematite into a mixture containing 93 % iron carbide and 7 % magnetite for the unpromoted catalyst and 81 % iron carbide and 19 % magnetite for the K‐promoted catalyst. Initially, the activated catalysts had high CO conversions (≈85 %); however, the conversions decreased to approximately 30 % after approximately 280 h of synthesis time. For the unpromoted catalyst, the amount of iron carbide gradually decreased over time while the corresponding magnetite phase increased. However, for the K‐promoted one, only one iron carbide phase (χ‐Fe5C2) gradually decreased, while the other ($\acute \epsilon $‐Fe2.2C) phase steadily increased and magnetite remained unchanged. TEM analyses revealed that for the K‐promoted catalyst, carbon deposition increased over time, unlike that of the unpromoted catalyst.
Influence of the Marangoni Effect on Mass Transfer in Inclined Falling Films
Authors: Zhang Huishu , Yuan Xigang , Yu Kuotsung , Kalbassi Mohammad Ali , Liu Botan
Published: June 2014

The Marangoni effect on the mass transfer coefficient of falling films was investigated on inclined stainless‐steel plates to elucidate the influence on the mass transfer performance of structured packing surfaces. Desorption of ethanol from water generated the Marangoni effect in the liquid phase while the process of oxygen desorption from water was proceeded. The enhanced liquid phase mass transfer by the Marangoni effect was found to be related to the ethanol concentration in the liquid, inclination of the plate, and liquid flow condition. A generalized correlation was proposed to predict the effective enhancement factor of the system incorporated with the Marangoni effect.
Effect of Structural Parameters on Drop Size Distribution in Pulsed Packed Columns
Authors: Samani Mahmoud Gholam , Safdari Jaber , Asl Ali Haghighi , Torab‐Mostaedi Meisam
Published: June 2014

The effect of packing type on drop size distribution in pulsed packed columns was investigated by means of different columns and three packing types with three liquid systems including n‐butyl acetate, toluene, and kerosene with water. These liquid systems cover a wide range of interfacial tensions. Also the influence of operating variables in terms of pulse intensity and volumetric flow rates of dispersed and continuous phases was examined. Pulse intensity, interfacial tension, and packing shape were found as the main important factors for drop size distribution while volumetric flow rates had no significant effect. Correlations are presented to predict drop distribution and mean drop size in pulsed packed columns.
Elimination of Perfluorinated Surfactants – Adsorbent Evaluation Applying Surface Tension Measurements
Authors: Schuricht Falk , Reschetilowski Wladimir , Reich Andy , Giebler Eckart
Published: June 2014

The adsorption of perfluorooctane sulfonate (PFOS) onto activated carbons, nonfunctionalized polymeric adsorbents, and anion exchange resins was evaluated in batch as well as column experiments. It was found that the total PFOS capacity, adsorption kinetics, breakthrough times, and minimum effluent concentrations were highly dependent on the material properties, such as the inner surface area, pore size, functionalization, and hydrophobic character of the material, and on process parameters like temperature and ionic strength of the solution. The experiments furthermore revealed that surface tension measurements are a suitable method for online determination of PFOS concentrations above a defined value.
Generation of Active Sites on Gold Nanostructured Surface through Ultrasound‐Assisted Direct Electrodeposition and Its Effect on Enzyme‐less Glucose Electro‐oxidation
Authors: Boopathi Sidhureddy , Senthil Kumar Shanmugam , Narasimha Phani Kanala Lakshmi
Published: June 2014

By using ultrasound‐assisted direct electrodeposition, gold nanostructured films decorated by catalytic sites can be generated that are capable of effecting enzyme‐less oxidation of glucose at pH 7.4. The morphology, surface roughness and nature of the crystallographic orientation of the deposited gold nanoparticles on a glassy carbon electrode surface are studied by atomic force microscopy and metal underpotential deposition. The cyclic voltammetry signatures of the deposited nanostructured gold films reveal the identity of the catalytically active sites, which undergo pre‐monolayer oxidation/reduction on the nanostructured gold surface. These active species are responsible for the electrocatalytic oxidation of glucose under neutral pH conditions, enabling a steady‐state amperometric response in a linear range of concentration from 0.25 to 1.75 mMwith a sensitivity of 0.849×10−3 mA cm−2 mM−1.
Sponge Phase Producing Porous CeO2 for Catalytic Oxidation of CO
Authors: Song Shasha , Wang Haiqiao , Song Aixin , Dong Shuli , Hao Jingcheng
Published: June 2014

The aggregation behavior of mixtures of the alkaline amino acid L‐Arginine (L‐Arg) and bis(2‐ethylhexyl)phosphoric acid (DEHPA) in water was studied in detail. At a fixed L‐Arg concentration, a phase sequence of micellar phase (L1 phase), vesicle phase (Lαv phase), planar lamellar phase (Lαl phase), and sponge phase (L3 phase) was obtained with increasing DEHPA concentration due to changes in the packing parameter. The phase transition of the lamellar structures was determined by freeze‐fracture TEM and 2H NMR spectroscopy. Rheological measurements reflected the phase transition through significant variations of both the elastic modulus and the viscous modulus. Porous CeO2 materials were produced by utilizing the L3 phase as template, and the porous CeO2 exhibited excellent catalytic oxidation activity toward CO due to its high surface area, which provides more active sites for CO conversion.
Fine‐Tuning Dual Emission and Aggregation‐Induced Emission Switching in NPI–BODIPY Dyads
Authors: Mukherjee Sanjoy , Thilagar Pakkirisamy
Published: June 2014

Three new NPI–BODIPY dyads 1–3 (NPI=1,8‐naphthalimide, BODIPY=boron‐dipyrromethene) were synthesized, characterized, and studied. The NPI and BODIPY moieties in these dyads are electronically separated by oxoaryl bridges, and the compounds only differ structurally with respect to methyl substituents on the BODIPY fluorophore. The NPI and BODIPY moieties retain their optical features in molecular dyads 1–3. Dyads 1–3 show dual emission in solution originating from the two separate fluorescent units. The variations of the dual emission in these compounds are controlled by the structural flexibilities of the systems. Dyads 1–3, depending on their molecular flexibilities, show considerably different spectral shapes and dissimilar intensity ratios of the two emission bands. The dyads also show significant aggregation‐induced emission switching (AIES) on formation of nano‐aggregates in THF/H2O with changes in emission color from green to red. Whereas the flexible and aggregation‐prone compound 1 shows AIES, rigid systems with less favorable intermolecular interactions (i.e., 2 and 3) show aggregation‐induced quenching of emission. Correlations of the emission intensity and structural flexibility were found to be reversed in solution and aggregated states. Photophysical and structural investigations suggested that intermolecular interactions (e.g., π–π stacking) play a major role in controlling the emission of these compounds in the aggregated state.
Tuning the Halogen/Hydrogen Bond Competition: A Spectroscopic and Conceptual DFT Study of Some Model Complexes Involving CHF2I
Authors: Nagels Nick , Geboes Yannick , Pinter Balazs , De Proft Frank , Herrebout Wouter A.
Published: June 2014

Insight into the key factors driving the competition of halogen and hydrogen bonds is obtained by studying the affinity of the Lewis bases trimethylamine (TMA), dimethyl ether (DME), and methyl fluoride (MF) towards difluoroiodomethane (CHF2I). Analysis of the infrared and Raman spectra of solutions in liquid krypton containing mixtures of TMA and CHF2I and of DME and CHF2I reveals that for these Lewis bases hydrogen and halogen‐bonded complexes appear simultaneously. In contrast, only a hydrogen‐bonded complex is formed for the mixtures of CHF2I and MF. The complexation enthalpies for the CH⋅⋅⋅Y hydrogen‐bonded complexes with TMA, DME, and MF are determined to be −14.7(2), −10.5(5) and −5.1(6) kJ mol−1, respectively. The values for the CI⋅⋅⋅Y halogen‐bonded isomers are −19.0(3) kJ mol−1 for TMA and −9.9(8) kJ mol−1 for DME. Generalization of the observed trends suggests that, at least for the bases studied here, softer Lewis bases such as TMA favor halogen bonding, whereas harder bases such as MF show a substantial preference for hydrogen bonding.
Hydride‐Rhodium(III)‐N‐Heterocyclic Carbene Catalysts for Vinyl‐Selective H/D Exchange: A Structure–Activity Study
Authors: Di Giuseppe Andrea , Castarlenas Ricardo , Pérez‐Torrente Jesús J. , Lahoz Fernando J. , Oro Luis A.
Published: June 2014

A series of neutral and cationic RhIII‐hydride and RhIII‐ethyl complexes bearing a NHC ligand has been synthesized and evaluated as catalyst precursors for H/D exchange of styrene using CD3OD as a deuterium source. Various ligands have been examined in order to understand how the stereoelectronic properties can modulate the catalytic activity. Most of these complexes proved to be very active and selective in the vinylic H/D exchange, without deuteration at the aromatic positions, displaying very high selectivity toward the β‐positions. In particular, the cationic complex [RhClH(CH3CN)3(IPr)]CF3SO3 showed excellent catalytic activity, reaching the maximum attainable degree of β‐vinylic deuteration in only 20 min. By modulation of the catalyst structure, we obtained improved α/β selectivity. Thus, the catalyst [RhClH(κ2‐O,N‐C9H6NO)(SIPr)], bearing an 8‐quinolinolate ligand and a bulky and strongly electron‐donating SIPr as the NHC, showed total selectivity for the β‐vinylic positions. This systematic study has shown that increased electron density and steric demand at the metal center can improve both the catalytic activity and selectivity. Complexes bearing ligands with very high steric hindrance, however, proved to be inactive.
Bis‐ and Tris(pyrazolyl)borate/Methane‐Stabilized PIII‐Centered Cations
Authors: Gu Lianghu , Gopakumar Gopinadhanpillai , Gualco Pauline , Thiel Walter , Alcarazo Manuel
Published: June 2014

We report the synthesis of [H2B(pz)2PR]+, [H2C(pz)2PR]+2, [HB(pz)3P]+2, and [HC(pz)3P]+3 (H2B(pz)2=bis(pyrazolyl)borate; H2C(pz)2=bis(pyrazolyl)methane; HB(pz)3=tris(pyrazolyl)borate; HC(pz)3=tris(pyrazolyl) methane; R=Ph, Cy or Et2N) by reaction of the corresponding neutral or anionic ligands with chlorophosphines in the presence of TMSOTf. The structures of these compounds were determined by X‐ray crystallographic analysis and the nature of their bonding was examined using density functional theory.
Hydroalumination of a Chlorotrialkynylsilane: Spontaneous Stepwise 1,3‐Dyotropic Rearrangement via an Intermediate Silyl Cation
Authors: Uhl Werner , Bohnemann Jörg , Layh Marcus , Würthwein Ernst‐Ulrich
Published: June 2014

A new functionalised alkynylsilane, Cl‐Si(CC‐CMe3)3 (3), was obtained by a facile multistep synthesis. Treatment of 3 with equimolar quantities of the hydrides H‐M(CMe3)2 (M=Al, Ga) gave the mixed alkenyl‐di(alkynyl)silanes, in which the chlorine atom adopts a bridging position between the aluminium and silicon atoms. Dual hydrogallation of 3 resulted in the formation of a di(alkenyl)‐alkynylsilane containing two gallium atoms, one of which is coordinated to the chlorine atom, and the second is bonded to the α‐carbon atom of the remaining alkynyl group. A tert‐butylsilane was unexpectedly formed by a unique 1,3‐dyotropic chlorine–tert‐butyl exchange for the corresponding dialuminium compound. One aluminium atom is bonded to a tert‐butyl group, a terminal chlorine atom and the α‐carbon atom of the ethynyl moiety; the second is coordinatively unsaturated, with two terminal tert‐butyl substituents. High‐level quantum‐chemical calculations favour a stepwise dyotropic rearrangement with an intermediate cationic silicon species over a simultaneous tert‐butyl–chlorine migration via a five‐coordinate silicon atom in the transition state.
The Mixed Gold–Palladium Polyoxo‐Noble‐Metalate [NaAuIII4PdII8O8(AsO4)8]11−
Authors: Izarova Natalya V. , Kondinski Aleksandar , Vankova Nina , Heine Thomas , Jäger Patrick , Schinle Florian , Hampe Oliver , Kortz Ulrich
Published: June 2014

The first fully inorganic, discrete gold–palladium–oxo complex [NaAuIII4PdII8O8(AsO4)8]11− has been synthesized in aqueous medium. The combination of single‐crystal XRD, elemental analysis, mass spectrometry, and DFT calculations allowed establishing the structure and composition of the novel polyanion, and UV/Vis studies suggest that it is stable in neutral aqueous media.
Primary Malignancies of the Heart and Pericardium
Authors: Burazor Ivana , Aviel‐Ronen Sarit , Imazio Massimo , Markel Gal , Grossman Yoni , Yosepovich Ady , Adler Yehuda
Published: June 2014

Primary malignancies of the heart and pericardium are rare. All the available data come from autopsy studies, case reports, and, in recent years, from large, specialized, single‐center studies. Nevertheless, if primary malignancy is present, it may have a devastating implication for patients. Malignancies may affect heart function, also causing left‐sided or right‐sided heart failure. In addition, they can be responsible for embolic events or arrhythmias. Today, with the widespread use of noninvasive imaging modalities, heart tumors become evident, even as an incidental finding. A multimodality imaging approach is usually required to establish the final diagnosis. Despite the increased awareness and improved diagnostic techniques, clinical manifestations of primary malignancy of the heart and pericardium are so variable that their occurrence may still come as a surprise during surgery or autopsy. No randomized clinical trials have been carried out to determine the optimal therapy for these primary malignancies. Surgery is performed for small tumors. Chemotherapy and radiation therapy can be of help. Partial resection of large neoplasms is performed to relieve mechanical effects, such as cardiac compression or hemodynamic obstruction. Most patients present with marginally resectable or technically nonresectable disease at the time of diagnosis. It seems that orthotopic cardiac transplantation with subsequent immunosuppressive therapy may represent an option for very carefully selected patients. Early diagnosis and radical exeresis are of great importance for long‐term survival of a primary cardiac malignancy. This can rarely be accomplished, and overall results are very disappointing.
Synthesis, σ Receptor Affinity, and Pharmacological Evaluation of 5‐Phenylsulfanyl‐ and 5‐Benzyl‐Substituted Tetrahydro‐2‐benzazepines
Authors: Hasebein Peer , Frehland Bastian , Schepmann Dirk , Wünsch Bernhard
Published: June 2014

In accordance with a novel strategy for generating the 2‐benzazepine scaffold by connecting C6–C1 and C3–N building blocks, a set of 5‐phenylsulfanyl‐ and 5‐benzyl‐substituted tetrahydro‐2‐benzazepines was synthesized and pharmacologically evaluated. Key steps of the synthesis were the Heck reaction, the Stetter reaction, a reductive cyclization, and the introduction of diverse N substituents at the end of the synthesis. High σ1 affinity was achieved for 2‐benzazepines with linear or branched alk(en)yl residues containing at least an n‐butyl substructure. The butyl‐ and 4‐fluorobenzyl‐substituted derivatives, (±)‐5‐benzyl‐2‐butyl‐2,3,4,5‐tetrahydro‐1H‐2‐benzazepine (19 b) and (±)‐5‐benzyl‐2‐(4‐fluorobenzyl)‐2,3,4,5‐tetrahydro‐1H‐2‐benzazepine (19 m), show high selectivity over more than 50 other relevant targets, including the σ2 subtype and various binding sites of the N‐methyl‐D‐aspartate (NMDA) receptor. In the Irwin screen, 19 b and 19 m showed clean profiles without inducing considerable side effects. Compounds 19 b and 19 m did not reveal significant analgesic and cognition‐enhancing activity. Compound 19 m did not have any antidepressant‐like effects in mice.
Do patients with advanced cancer value the physical examination?
Authors: Hunt Daniel P.
Published: June 2014

Patients with advanced cancer still value the physical examination, according to the study by Kadakia et al. The exam serves both pragmatic and symbolic purposes for patients.
Management of the lymph node‐positive neck in the patient with human papillomavirus‐associated oropharyngeal cancer
Authors: Garden Adam S. , Gunn Gary B. , Hessel Amy , Beadle Beth M. , Ahmed Salmaan , El‐Naggar Adel K. , Fuller Clifton D. , Byers Lauren A. , Phan Jack , Frank Steven J. , Morrison William H. , Kies Merill S. , Rosenthal David I. , Sturgis Erich M.
Published: June 2014

BACKGROUND

The goal of the current study was to assess the rates of recurrence in the neck for patients with lymph node‐positive human papillomavirus‐associated cancer of the oropharynx who were treated with definitive radiotherapy (with or without chemotherapy).

METHODS

This is a single‐institution retrospective study. Methodology included database search, and statistical testing including frequency analysis, Kaplan‐Meier tests, and comparative tests including chi‐square, logistic regression, and log‐rank.

RESULTS

The cohort consisted of 401 patients with lymph node‐positive disease who underwent radiotherapy between January 2006 and June 2012. A total of 388 patients had computed tomography restaging, and 251 had positron emission tomography and/or ultrasound as a component of their postradiation staging. Eighty patients (20%) underwent neck dissection, and 21 patients (26%) had a positive specimen. The rate of neck dissection increased with increasing lymph node stage, and was lower in patients who had positron emission tomography scans or ultrasound in addition to computed tomography restaging. The median follow‐up was 30 months. The 2‐year actuarial neck recurrence rate was 7% and 5%, respectively, in all patients and those with local control. Lymph node recurrence rates were greater in current smokers (P = .008). There was no difference in lymph node recurrence rates noted between patients who did and those who did not undergo a neck dissection (P = .4)

CONCLUSIONS

A treatment strategy of (chemo)radiation with neck dissection performed based on response resulted in high rates of regional disease control in patients with human papillomavirus‐associated oropharyngeal cancer. Cancer 2014;120:3082–3088. © 2014 American Cancer Society.
Fluorescence Microscopy with 6 nm Resolution on DNA Origami
Authors: Raab Mario , Schmied Jürgen J. , Jusuk Ija , Forthmann Carsten , Tinnefeld Philip
Published: June 2014

Resolution of emerging superresolution microscopy is commonly characterized by the width of a point‐spread‐function or by the localization accuracy of single molecules. In contrast, resolution is defined as the ability to separate two objects. Recently, DNA origamis have been proven as valuable scaffold for self‐assembled nanorulers in superresolution microscopy. Here, we use DNA origami nanorulers to overcome the discrepancy of localizing single objects and separating two objects by resolving two docking sites at distances of 18, 12, and 6 nm by using the superresolution technique DNA PAINT(point accumulation for imaging in nanoscale topography). For the smallest distances, we reveal the influence of localization noise on the yield of resolvable structures that we rationalize by Monte Carlo simulations.
Studies on drug metabolism by fungi colonizing decomposing human cadavers. Part II: biotransformation of five model drugs by fungi isolated from post‐mortem material
Authors: Martínez‐Ramírez Jorge A. , Walther Grit , Peters Frank T.
Published: June 2014

The present study investigated thein vitrometabolic capacity of 28 fungal strains isolated from post‐mortem material towards five model drugs: amitriptyline, metoprolol, mirtazapine, promethazine, and zolpidem. Each fungal strain was incubated at 25 °C for up to 120 h with each of the five models drugs.Cunninghamella eleganswas used as positive control. Aliquots of the incubation mixture were centrifuged and 50 μL of the supernatants were diluted and directly analyzed by liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) with product ion scanning. The remaining mixture was analyzed by full scan gas chromatography‐mass spectrometry (GC‐MS) after liquid‐liquid extraction and acetylation. The metabolic activity was evaluated through the total number of detected metabolites (NDM) produced in each model and fungal strains and the percentage of parent drug remaining (%RPD) after up to five days of incubation. All the tested fungal strains were capable of forming mammalian phase I metabolites. Fungi from the normal fungal flora of the human body such asCandidasp., Geotrichum candidum,andTrichosporon asahii) formed up to seven metabolites at %RPD values greater than 52% but no new fungal metabolites (NFM). In contrast, some airborne fungal strains likeBjerkandera adusta, Chaetomium sp, Coriolopsis sp., Fusarium solaniandMucor plumbeusshowed NDM values exceeding those of the positive control, complete metabolism of the parent drug in some models and formation of NFM. NFM (numbers in brackets) were detected in four of the five model drugs: amitriptyline (18), metoprolol (4), mirtazapine (8), and zolpidem (2). The latter NFM are potential candidates for marker substances indicating post‐mortem fungal metabolism. Copyright © 2014 John Wiley & Sons, Ltd.
Structures and Magnetic Properties of Group 13 Metal Tris‐O‐benzosemiquinonato Complexes
Authors: Piskunov Alexandr V. , Meshcheryakova Irina N. , Maleeva Arina V. , Bogomyakov Artyem S. , Fukin Georgy K. , Cherkasov Vladimir K. , Abakumov Gleb A.
Published: June 2014

New tris‐o‐benzosemiquinonato complexes of Al, Ga, and In based on the sterically hindered o‐benzoquinone 5,8‐di‐tert‐butyl‐2,3‐dihydro‐1,4‐ethanoquinoxaline‐6,7‐dione (NN‐3,6‐Q) were synthesized. The structures of the hexacoordinate metal compounds were investigated by X‐ray diffraction. The magnetic properties of the complexes obtained were found to be strongly dependent on their molecular geometry. The octahedral Al and Ga derivatives demonstrate ferromagnetic exchange between the magnetic centers, whereas the trigonal‐prismatic In complex shows an antiferromagnetic coupling.
Photosensitizing Properties of Alkynylrhenium(I) Complexes [Re(–C≡C–R)­(CO)3(N∩N)] (N∩N = 2,2′‐bipy, phen) for H2 Production
Authors: Oberholzer Miriam , Probst Benjamin , Bernasconi Dominik , Spingler Bernhard , Alberto Roger
Published: June 2014

A series of complexes of the type [fac‐Re(X)(CO)3(N∩N)] (X = –C≡C–R, N∩N = 2,2′‐bipy, 2,2′‐phen) were synthesized and fully characterized. Their photophysical characteristics make them very convenient photosensitizers (PSs). Upon light irradiation, H2 formation was observed for all alkynyl complexes in the presence of a water‐reducing catalyst (WRC) and a sacrificial electron donor. Relative rates of H2 production indicate a dependency upon the diimine ligands rather than upon the nature of the σ‐bonded alkynyl derivatives. The coordinated acetylene group induces a redshift of the λmax of the MLCT band in UV/Vis spectroscopy as compared to those of the corresponding halides, nitriles, or cationic ReI complexes, such as [fac‐ReX(CO)3(N∩N)] (X = pyridine, H2O, N∩N = bipy, phen).
Metallo‐β‐lactamases and Their Biomimetic Complexes
Authors: Daumann Lena J. , Schenk Gerhard , Gahan Lawrence R.
Published: June 2014

In order to treat bacterial infections successfully in the future, the mechanism of action of metallo‐β‐lactamases (MβLs) needs to be fully understood so that clinically useful inhibitors and new therapeutic approaches can be developed. This microreview describes recent developments and the achievements towards the design of MβL biomimetics to aid in the mechanistic and structural understanding of these enzyme systems. We highlight the known inhibitors and substrates employed in these studies, the different ligands and complexes employed, and the experimental and computational studies undertaken to explore the possible mechanisms of action of the MβLs.
Organotantalum Phosphaketene and Phosphaazaallene Complexes
Authors: Grundmann Anne , Sárosi Menyhárt B. , Lönnecke Peter , Hey‐Hawkins Evamarie
Published: June 2014

The first tantalum phosphaketene and phosphaazaallene complexes [Cp*Ta{1,2‐(NSiMe3)2C6H4}{P(R)CX}] {Cp* = C5Me5; X = O; R = cyclohexyl (Cy, 3), iPr (4); X = NCy, R = Cy (5), iPr (6)} were obtained by insertion of carbon monoxide or cyclohexyl isocyanide into the Ta–P bond of cyclohexyl‐ and (isopropylphosphanylidene)tantalum(V) complexes, [Cp*Ta{1,2‐(NSiMe3)2C6H4}(PR)] {R = Cy (1), iPr (2)}. Phosphaazaallene complexes 5 and 6 occur as E and Z isomers. These isomers have different electronic structures according to NMR spectroscopic studies and DFT calculation. Both isomers of the cyclohexylphosphanyl derivative (i.e., 5a and 5b) and one isomer of the isopropylphosphanyl derivative (i.e., 6b) could be structurally characterized by X‐ray crystallography.
Vanadium Complexes as Prospective Therapeutics: Structural Characterization of a VIV Lysozyme Adduct
Authors: Santos Marino F. A. , Correia Isabel , Oliveira Ana R. , Garribba Eugenio , Pessoa João Costa , Santos‐Silva Teresa
Published: June 2014

The biological activity of vanadium complexes, namely, as insulin enhancers, is well known. We report a combined X‐ray crystallography, electron paramagnetic resonance, and density functional theory study of the interaction of vanadium picolinate complexes with hen egg white lysozyme (HEWL). We show that the VIVO(pic)2 complex covalently binds to the COO– group of the side chain of Asp52 of HEWL. The long VIV=O bond obtained in the X‐ray study is explained to be due to reduction of VIV to VIII during exposure of the crystals to the intense X‐ray beam.
Synthesis and Evaluation of Polyunsaturated Fatty Acid–Phenol Conjugates as Anti‐Carbonyl‐Stress Lipophenols
Authors: Crauste Céline , Vigor Claire , Brabet Philippe , Picq Madeleine , Lagarde Michel , Hamel Christian , Durand Thierry , Vercauteren Joseph
Published: June 2014

Carbonyl and oxidative stress play a substantial role in various neurodegenerative diseases such as Alzheimer's Disease, Parkinsonism, and Age‐related Macular Degeneration (AMD). In retinal pathologies, both mechanisms are involved in the transformation of all‐trans‐retinal (AtR, reactive aldehyde) into bis‐retinoid A2E. Since an accumulation of AtR and A2E contributes to photoreceptor apoptosis, we designed and synthesized a series of O‐alkylated resorcinol derivatives featuring enhanced anti‐carbonyl‐stress properties. Additionally, these phenolic structures are linked to a polyunsaturated fatty acid such as docosahexaenoic acid (C22:6 n‐3; DHA) or to a lysophosphatidylcholine–DHA conjugate, in order to specifically increase their bioavailability, and thus, to target the retina. Selective syntheses of phloroglucinol–DHA, resveratrol–DHA, and phloroglucinol–DHA–PC (PC = phosphatidylcholine) conjugates using silyl protecting group strategies are presented, along with results of testing that demonstrate their ability to lower AtR toxicity in ARPE‐19 cell lines.
Resveratrol production at large scale using plant cell suspensions
Authors: Jeandet Philippe , Clément Christophe , Courot Eric
Published: June 2014

Resveratrol and its derivatives are a class of polyphenolic compounds recognized for their outstanding biological properties based on clinical trials. In addition, their possible uses in nutraceutics, cosmetics, and as pharmaceutics create a need for large‐scale production with the possibility to use sustainable sources. In this review, we report on the biotechnological production of resveratrol and some of its derivatives through plant cell suspensions, such as grapevine cell culture systems. These cultures usually need elicitation. Methyljasmonate, cyclodextrins, the combination of both and chitosan are the elicitors leading to the best responses in terms of resveratrol amounts produced in flasks. Production performances of resveratrol can be optimized in flasks for scale‐up in large culture volumes. We summarize the plant cell culture systems used for resveratrol bioproduction and transfer experiments from flasks to bioreactors as well as elicitor‐mediated upregulation of the defense genes in those plant culture systems.