bluuebunny/crossref_metadata_2025 huggingface dataset:
On the Quest of Dioxygen by Monomeric Sarcosine Oxidase. A Molecular Dynamics Investigation
Authors: Pietra Francesco
Published: August 2015

It is reported here on random acceleration molecular dynamics (RAMD) simulations with the 2GF3 bacterial monomeric sarcosine oxidase (MSOX), O2, and furoic acid in place of sarcosine, solvated by TIP3 H2O in a periodic box. An external tiny force, acting randomly on O2, accelerated its relocation, from the center of activation between residue K265 and the si face of the flavin ring of the flavin adenine dinucleotide cofactor, to the surrounding solvent. Only three of the four O2 gates previously described for this system along a composite method technique were identified, while two more major O2 gates were found. The RAMD simulations also revealed that the same gate can be reached by O2 along different pathways, often involving traps for O2. Both the residence time of O2 in the traps, and the total trajectory time for O2 getting to the solvent, could be evaluated. The new quick pathways discovered here suggest that O2 exploits all nearby interstices created by the thermal fluctuations of the protein, not having necessarily to look for the permanent large channel used for uptake of the FADH cofactor. To this regard, MSOX resembles closely KijD3 N‐oxygenase. These observations solicit experimental substantiation, in a long term aim at discovering whether gates and pathways for the small gaseous ligands inside the proteins are under Darwinian functional evolution or merely stochastic control operates.
Effects of Organic Modifiers on a Palladium Catalyst in the Competitive Hydrogenation of 1‐Octene Versus Octanal: An Evaluation of Solid Catalysts with an Ionic Liquid Layer
Authors: Miller Stuart F. , Friedrich Holger B. , Holzapfel Cedric W. , Dasireddy Venkata D. B. C.
Published: August 2015

The competitive hydrogenation between 1‐octene and octanal has been investigated with a ≈5 % palladium on alumina catalyst prepared in situ with the following organic modifiers: pyridine, 1‐methylimidazole, 1,3‐dimethylimidazole methylsulfate, 1,3‐dimethylimidazole bis(trifluoromethylsulfonyl)imide and methyltri‐sec‐butylphosphonium methylsulfate. The results of these investigations indicate that the ionic liquid modifiers have significant and specific effects on catalytic performance, for example, certain systems can completely suppress octanal conversion. In addition, analytical techniques reveal that the matrix and quantity of organic species on the used catalysts are different if different ionic liquids are used as modifiers. Surface studies also reveal that the modifiers have a noticeable effect on the crystallite size and chemisorption properties of the catalysts.
Effect of Electrolyte pH on the Inherent Electrochemistry of Layered Transition‐Metal Dichalcogenides (MoS2, MoSe2, WS2, WSe2)
Authors: Zafir Mohamad Nasir Muhammad , Sofer Zdeněk , Pumera Martin
Published: August 2015

We set forth to investigate the changes in the inherent oxidative peaks of different transition‐metal dichalcogenides (TMDs), namely MoS2, MoSe2, WS2, and WSe2, at different electrolyte pH values. Changing the pH of the electrolyte was found to influence and affect the inherent oxidation of TMDs, more noticeably the peak position. This could be attributed to the different reaction mechanisms and stability at the different pH values. An increase in the electrolyte pH from 0 to 8 shows a linear decrease in the peak potentials of the inherent oxidative peaks. However, small changes in peak potentials were observed at low alkaline pH levels (from 8 to 11). Beyond pH 11, the emergence of an additional peak at low potentials, apart from the inherent oxidative peak, was observed for most of the TMD materials studied. This insight into the pH dependence of the oxidation of TMD materials is of paramount importance for their electrochemical applications.
A Renewable Display Platform Based on the Bipolar Electrochromic Electrode
Authors: Zhang Xiaowei , Shang Changshuai , Gu Wenlin , Xia Yong , Li Jing , Wang Erkang
Published: August 2015

We report a renewable display platform based on bipolar electrochemistry that uses bipolar electrochromic electrode (BP‐EC‐E) arrays for high‐throughput screening applications. Prussian blue (or another electrochromic material) is electrodeposited on one end of the bipolar electrode (BPE) as the signal reporter, and the other end is for the loading of catalyst. Owing to the quantitative relation between the two reactions occurring at both ends of the BP‐EC‐E, the discoloration speeds (Prussian blue to Prussian white) are related to the amount or the catalytic activity of the catalysts. Interestingly, the established platform can be used repeatedly, owing to the reversibility of the electrochromic reactions. With this strategy, we have achieved the fast imaging analysis of several electrocatalysts for methanol and ethanol oxidation.
Decoration of Hydrophobic Graphene Nanosheets with Iron Phosphate Based Materials in an Aqueous Solution
Authors: Kim Hyun‐Kyung , Jegal Jong‐Pil , Kim Myeong Seong , Roh Kwang Chul , Kim Kwang‐Bum
Published: August 2015

The surfaces of hydrophobic graphene nanosheets (GNs) are successfully decorated, aided by urea, with FePO4‐based materials in an aqueous solution. The hydrophobic GNs can easily disperse in the aqueous solution without functionalization in the presence of urea, leading to the formation of a GNs‐based nanocomposite with minimal sacrifice of the electrical conductivity of the GNs. Compared with reduced graphene oxide (rGO) decorated with FePO4⋅H2O (FePO4⋅H2O/rGO), synthesized using a graphene oxide (GO) substrate, the resulting FePO4⋅H2O/GNs nanocomposite exhibit superior rate performance, because the GNs have a higher C/O ratio than the rGO. In addition, LiFePO4/GNs with high coulombic efficiency and energy efficiency, prepared using FePO4⋅H2O/GNs, deliver a discharge capacity of 62 mAh g−1 at 120 C rate. Furthermore, a full cell consisting of LiFePO4/GNs and Li4Ti5O12/graphene exhibits excellent rate performance up to 60 C rate.
Difluorenyl carbo‐Benzenes: Synthesis, Electronic Structure, and Two‐Photon Absorption Properties of Hydrocarbon Quadrupolar Chromophores
Authors: Baglai Iaroslav , de Anda‐Villa Manuel , Barba‐Barba Rodrigo M. , Poidevin Corentin , Ramos‐Ortíz Gabriel , Maraval Valérie , Lepetit Christine , Saffon‐Merceron Nathalie , Maldonado José‐Luis , Chauvin Remi
Published: August 2015

The synthesis, crystal and electronic structures, and one‐ and two‐photon absorption properties of two quadrupolar fluorenyl‐substituted tetraphenyl carbo‐benzenes are described. These all‐hydrocarbon chromophores, differing in the nature of the linkers between the fluorenyl substituents and the carbo‐benzene core (CC bonds for 3 a, CCCC expanders for 3 b), exhibit quasi–superimposable one‐photon absorption (1PA) spectra but different two‐photon absorption (2PA) cross‐sections σ2PA. Z‐scan measurements (under NIR femtosecond excitation) indeed showed that the CC expansion results in an approximately twofold increase in the σ2PA value, from 336 to 656 GM (1 GM=10−50 cm4 s molecule−1 photon−1) at λ=800 nm. The first excited states of Au and Ag symmetry accounting for 1PA and 2PA, respectively, were calculated at the TDDFT level of theory and used for sum‐over‐state estimations of σ2PA(λi), in which λi=2 hc/Ei, h is Planck’s constant, c is the speed of light, and Ei is the energy of the 2PA‐allowed transition. The calculated σ2PA values of 227 GM at 687 nm for 3 a and 349 GM at 708 nm for 3 b are in agreement with the Z‐scan results.
Single‐Crystal‐to‐Single‐Crystal Transition in an Enantiopure [7]Helquat Salt: The First Observation of a Reversible Phase Transition in a Helicene‐Like Compound
Authors: Nath Naba K. , Severa Lukáš , Kunetskiy Roman A. , Císařová Ivana , Fulem Michal , Růžička Květoslav , Koval Dušan , Kašička Václav , Teplý Filip , Naumov Panče
Published: August 2015

Here it is reported that crystals of an enantiopure [7]helquat salt undergo reversible thermal solid–solid phase transition at 404 K. Differential scanning calorimetry (DSC), capillary electrophoresis (CE), and X‐ray diffraction analysis were used to unravel the mechanistic details of this process. The single‐crystal‐to‐single‐crystal course enabled direct monitoring of the structural changes by in situ variable‐temperature X‐ray diffraction, thus providing the first direct evidence of a solid phase transition in a helicene‐like compound.
Synthesis and Characterization of Dibenzo[a,d]cyclohepten‐5‐one Derivatives for Light‐Emitting Diodes
Authors: Wang Liping , Wang Limin , Huang Jianyao , Yu Gui
Published: August 2015

Three novel dibenzo[a,d]cyclohepten‐5‐one derivatives containing hole‐transporting groups were synthesized and characterized. These compounds exhibit good thermal stabilities. Single crystals of DBHO‐TPA and DBHO‐DPA were successfully grown from dichloromethane and their crystal structures were determined from X‐ray diffraction data. Two molecules, DBHO‐TPA and DBHO‐DPA, have a nonplanar structure while seven‐membered ring comprised in dibenzo[a,d]cyclohepten‐5‐one is not planar. Electrochemical properties of three compounds indicate that the different substituents on 3,7‐positions of the dibenzo[a,d]cyclohepten‐5‐one derivatives have a small effect on the energy levels of the highest occupied molecular orbitals. The blue‐green light‐emitting diodes based on dibenzo[a,d]cyclohepten‐5‐one derivatives were fabricated.
A Fluorescent Probe for Hg2+ Based on Gold(I) Complex with An Aggregation‐Induced Emission Feature
Authors: Han Xie , Lü Xiaoyi , Chen Zhao , Yu Guangao , Yin Jun , Liu Shenghua
Published: August 2015

A gold(I) complex that exhibited aggregation‐induced emission in acetonitrile‐water mixtures was designed. It showed high selectivity and sensitivity for Hg2+ in acetonitrile‐H2O (1:1, V:V) solution. Dynamic light scattering measurements were conducted to verify that the addition of Hg2+ changed the particle size and induced fluorescence quenching.
Occurrence and Emergency Response of 2‐Methylisoborneol and Geosmin in a Large Shallow Drinking Water Reservoir
Authors: Liu Hongbo , Pan Ding , Zhu Mengling , Zhang Dong
Published: August 2015

Taste and odor causing compounds (TOCCs) especially 2‐methylisoborneol (MIB) and geosmin (GSM) should be eliminated because of increasing complaints of undesirable musty and earthy odor in drinking water. Spatial and temporal distributions of MIB and GSM in a large shallow drinking water reservoir were investigated since its first filling. The results showed that the GSM concentration was <15 ng/L and its potential to cause a taste and odor event was small. The concentrations of MIB in the transition zone were higher than in the riverine and the lacustrine zones of the reservoir and could reach 330 ng/L during warmer seasons, which was an alarm for taste and odor events. Emergency response practices showed that (i) powdered activated carbon was effective in removing MIB while the raw water was flowing through the pipes to the drinking water treatment plants (DWTPs); (ii) the ozone‐biological activated carbon process was effective in removing MIB in DWTPs; and (iii) the combination of these two technologies could ensure that the MIB content in treated water stayed below the olfactory threshold concentration even when its concentration in the reservoir was >300 ng/L. Continuous monitoring of TOCCs not only provides water quality information to the reservoir operators but also shows the development of TOCCs, which would help researchers and engineers to find effective ways preventing the occurrence of TOCCs in drinking water.
Connexin 43‐targeted T1 contrast agent for MRI diagnosis of glioma
Authors: Abakumova Tatiana , Abakumov Maxim , Shein Sergey , Chelushkin Pavel , Bychkov Dmitry , Mukhin Vladimir , Yusubalieva Gaukhar , Grinenko Nadezhda , Kabanov Alexander , Nukolova Natalia , Chekhonin Vladimir
Published: August 2015

Glioblastoma multiforme is the most aggressive form of brain tumor. Early and accurate diagnosis of glioma and its borders is an important step for its successful treatment. One of the promising targets for selective visualization of glioma and its margins is connexin 43 (Cx43), which is highly expressed in reactive astrocytes and migrating glioma cells. The purpose of this study was to synthesize a Gd‐based contrast agent conjugated with specific antibodies to Cx43 for efficient visualization of glioma C6 in vivo. We have prepared stable nontoxic conjugates of monoclonal antibody to Cx43 and polylysine–DTPA ligands complexed with Gd(III), which are characterized by higher T1 relaxivity (6.5 mM−1 s−1 at 7 T) than the commercial agent Magnevist® (3.4 mM−1 s−1). Cellular uptake of Cx43‐specific T1 contrast agent in glioma C6 cells was more than four times higher than the nonspecific IgG‐contrast agent, as detected by flow cytometry and confocal analysis. MRI experiments showed that the obtained agents could markedly enhance visualization of glioma C6 in vivo after their intravenous administration. Significant accumulation of Cx43‐targeted contrast agents in glioma and the peritumoral zone led not only to enhanced contrast but also to improved detection of the tumor periphery. Fluorescence imaging confirmed notable accumulation of Cx43‐specific conjugates in the peritumoral zone compared with nonspecific IgG conjugates at 24 h after intravenous injection. All these features of Cx43‐targeted contrast agents might be useful for more precise diagnosis of glioma and its borders by MRI. Copyright © 2015 John Wiley & Sons, Ltd.
CUDA‐quicksort: an improved GPU‐based implementation of quicksort
Authors: Manca Emanuele , Manconi Andrea , Orro Alessandro , Armano Giuliano , Milanesi Luciano
Published: August 2015

Sorting is a very important task in computer science and becomes a critical operation for programs making heavy use of sorting algorithms. General‐purpose computing has been successfully used on Graphics Processing Units (GPUs) to parallelize some sorting algorithms. Two GPU‐based implementations of the quicksort were presented in literature: the GPU‐quicksort, a compute‐unified device architecture (CUDA) iterative implementation, and the CUDA dynamic parallel (CDP) quicksort, a recursive implementation provided by NVIDIA Corporation. We propose CUDA‐quicksort an iterative GPU‐based implementation of the sorting algorithm. CUDA‐quicksort has been designed starting from GPU‐quicksort. Unlike GPU‐quicksort, it uses atomic primitives to perform inter‐block communications while ensuring an optimized access to the GPU memory. Experiments performed on six sorting benchmark distributions show that CUDA‐quicksort is up to four times faster than GPU‐quicksort and up to three times faster than CDP‐quicksort. An in‐depth analysis of the performance between CUDA‐quicksort and GPU‐quicksort shows that the main improvement is related to the optimized GPU memory access rather than to the use of atomic primitives. Moreover, in order to assess the advantages of using the CUDA dynamic parallelism, we implemented a recursive version of the CUDA‐quicksort. Experimental results show that CUDA‐quicksort is faster than the CDP‐quicksort provided by NVIDIA, with better performance achieved using the iterative implementation. Copyright © 2015 John Wiley & Sons, Ltd.
Surface‐Enhanced Raman Scattering Based on Controllable‐Layer Graphene Shells Directly Synthesized on Cu Nanoparticles for Molecular Detection
Authors: Qiu Hengwei , Huo Yanyan , Li Zhen , Zhang Chao , Chen Peixi , Jiang Shouzhen , Xu Shicai , Ma Yong , Wang Shuyun , Li Hongsheng
Published: August 2015

Graphene shells with a controllable number of layers were directly synthesized on Cu nanoparticles (CuNPs) by chemical vapor deposition (CVD) to fabricate a graphene‐encapsulated CuNPs (G/CuNPs) hybrid system for surface‐enhanced Raman scattering (SERS). The enhanced Raman spectra of adenosine and rhodamine 6G (R6G) showed that the G/CuNPs hybrid system can strongly suppress background fluorescence and increase signal‐to‐noise ratio. In four different types of SERS systems, the G/CuNPs hybrid system exhibits more efficient SERS than a transferred graphene/CuNPs hybrid system and pure CuNPs and graphene substrates. The minimum detectable concentrations of adenosine and R6G by the G/CuNPs hybrid system can be as low as 10−8 and 10−10 M, respectively. The excellent linear relationship between Raman intensity and analyte concentration can be used for molecular detection. The graphene shell can also effectively prevent surface oxidation of Cu nanoparticles after exposure to ambient air and thus endow the hybrid system with a long lifetime. This work provides a basis for the fabrication of novel SERS substrates.
The 21st century cures act: Opportunities and challenges
Authors: Sarpatwari A , Kesselheim AS
Published: August 2015

On July 10, 2015, the U.S. House of Representatives overwhelmingly voted (344–77) to approve the 21st Century Cures Act, setting the stage for the Senate to consider its own version of the bill this fall. Such strong bipartisan support, rare in an age of congressional gridlock, might logically be interpreted as a sign of the Act's promise to foster innovative drug and device development. However, careful inspection reveals that while the Act contains some positive features, it represents a poor deal for Americans on balance that could result in the entry of more dangerous and ineffective drugs and devices onto the market and erode trust in the US Food and Drug Administration (FDA).
Therapeutic drug monitoring of monoclonal antibodies in inflammatory and malignant disease: Translating TNF‐α experience to oncology
Authors: Oude Munnink TH , Henstra MJ , Segerink LI , Movig KLL , Brummelhuis‐Visser P
Published: August 2015

Lack of response to monoclonal antibodies (mAbs) has been associated with inadequate mAb serum concentrations. Therapeutic drug monitoring (TDM) of mAbs has the potential to guide to more effective dosing in individual patients. This review discusses the mechanisms responsible for interpatient variability of mAb pharmacokinetics, summarizes exposure‐response data of mAbs used in inflammatory and malignant disease, presents current evidence of mAb‐TDM in inflammatory disease, and provides hurdles and required future steps for further implementing mAb‐TDM.
A 0.75‐V, 4‐μW, 15‐ppm/°C, 190 °C temperature range, voltage reference
Authors: Andreou Charalambos M. , Georgiou Julius
Published: August 2015

A low‐voltage, low‐power, low‐area, wide‐temperature‐range CMOS voltage reference is presented. The proposed reference circuit achieves a measured temperature drift of 15 ppm/°C for an extremely wide temperature range of 190 °C (−60 to 130 °C) while consuming only 4 μW at 0.75 V. It performs a high‐order curvature correction of the reference voltage while consisting of only CMOS transistors operating in subthreshold and polysilicon resistors, without utilizing any diodes or external components such as compensating capacitors. A trade‐off of this circuit topology, in its current form, is the high line sensitivity. The design was fabricated using TowerJazz semiconductor's 0.18‐µm standard CMOS technology and occupies an area of 0.039 mm2. The proposed reference circuit is suitable for high‐precision, low‐energy‐budget applications, such as mobile systems, wearable electronics, and energy harvesting systems. Copyright © 2015 John Wiley & Sons, Ltd.
Meta‐analytic research on the relationship between cumulative risk alleles and risk of type 2 diabetes mellitus
Authors: Kodama Satoru , Fujihara Kazuya , Ishiguro Hajime , Horikawa Chika , Ohara Nobumasa , Yachi Yoko , Tanaka Shiro , Shimano Hitoshi , Kato Kiminori , Hanyu Osamu , Sone Hirohito
Published: August 2015

Background

Our aim is to examine the dose–response association between cumulative genetic risk and actual risk of type 2 diabetes mellitus (T2DM) and the influence of adjustment for covariates on T2DM risk through a comprehensive meta‐analysis of observational studies.

Methods

Electronic literature search using EMBASE and MEDLINE (from 2003 to 2014) was conducted for cross‐sectional or longitudinal studies that presented the odds ratio (OR) for T2DM in each group with categories based on the total number of risk alleles (RAs) carried (RAtotal) using at least two single‐nucleotide polymorphisms. Spline regression model was used to determine the shape of the relationship between the difference from the referent group of each study in RAtotal (ΔRAtotal) and the natural logarithms of ORs (log OR) for T2DM.

Results

Sixty‐five eligible studies that included 68 267 cases among 182 603 participants were analysed. In both crude and adjusted ORs, defined by adjusting the risk for at least two confounders among age, gender and body mass index, the slope of the log OR for T2DM became less steep as the ΔRAtotal increased. In the analysis limited to 14 cross‐sectional and four longitudinal studies presenting both crude and adjusted ORs, regression curves of both ORs in relation to ΔRAtotal were almost identical.

Conclusion

Using only single‐nucleotide polymorphisms for T2DM screening was of limited value. However, when genotypic T2DM risk was considered independently from risk in relation to covariates, it was suggested that genetic profiles might have a supplementary role related to conventional T2DM risk factors in identifying individuals at high risk of T2DM. Copyright © 2015 John Wiley & Sons, Ltd.
Nitric oxide regulates antagonistically phagocytic and neurite outgrowth inhibiting capacities of microglia
Authors: Scheiblich Hannah , Bicker Gerd
Published: August 2015

Traumatic injury or the pathogenesis of some neurological disorders is accompanied by inflammatory cellular mechanisms, mainly resulting from the activation of central nervous system (CNS) resident microglia. Under inflammatory conditions, microglia up‐regulate the inducible isoform of NOS (iNOS), leading to the production of high concentrations of the radical molecule nitric oxide (NO). At the onset of inflammation, high levels of microglial‐derived NO may serve as a cellular defense mechanism helping to clear the damaged tissue and combat infection of the CNS by invading pathogens. However, the excessive overproduction of NO by activated microglia has been suggested to govern the inflammation‐mediated neuronal loss causing eventually complete neurodegeneration. Here, we investigated how NO influences phagocytosis of neuronal debris by BV‐2 microglia, and how neurite outgrowth of human NT2 model neurons is affected by microglial‐derived NO. The presence of NO greatly increased microglial phagocytic capacity in a model of acute inflammation comprising lipopolysaccharide (LPS)‐activated microglia and apoptotic neurons. Chemical manipulations suggested that NO up‐regulates phagocytosis independently of the sGC/cGMP pathway. Using a transwell system, we showed that reactive microglia inhibit neurite outgrowth of human neurons via the generation of large amounts of NO over effective distances in the millimeter range. Application of a NOS blocker prevented the LPS‐induced NO production, totally reversed the inhibitory effect of microglia on neurite outgrowth, but reduced the engulfment of neuronal debris. Our results indicate that a rather simple notion of treating excessive inflammation in the CNS by NO synthesis blocking agents has to consider functionally antagonistic microglial cell responses during pharmaceutic therapy. © 2015 Wiley Periodicals, Inc. Develop Neurobiol 76: 566–584, 2016
Latest Devonian to earliest Carboniferous conodont and carbon isotope stratigraphy of a shallow‐water sequence in South China
Authors: Qie Wenkun , Wang Xiang‐Dong , Zhang Xionghua , Ji Wenting , Grossman Ethan L. , Huang Xing , Liu Jiangsi , Luo Genming
Published: August 2015

To improve regional and intercontinental correlation of the uppermost Devonian–lowermost Carboniferous, we examined the conodont faunas and carbon isotopic records of the Tangbagou Formation in the Qilinzhai section, southern Guizhou, South China. The Tangbagou Formation is a succession of mixed carbonate–siliciclastic rocks that accumulated on a shallow‐water platform under normal marine conditions. Seven conodont zones for shallow‐water biofacies in South China, theCl.gilwernensis–Cl.unicornisZone, thePo.spicatusZone, theSi.homosimplexZone, theSi.sinensisZone, theSi.eurylobataZone, thePs.multistriatusZone and thePo.co.porcatusZone in ascending order, are recognized in the Tangbagou Formation. Although apparently limited in its value for global correlation, this conodont zonation is more applicable to shallow‐water biofacies in South China. Carbonate samples have yielded carbon isotopic signatures consistent with those recorded in Euroamerica sections, in particular showing four distinct characteristics: (1) the peak values of Hangenberg Carbon Isotope Excursion (HICE) during the latest Devonian, (2) a minor positive shift (P1) in theSi.homosimplexZone during the early Tournaisian, (3) a second minor positive shift (P2) in theSi.sinensisZone and (4) the middle Tournaisian Carbon Isotope Excursion (TICE) in the middle part of the Tangbagou Formation. The similarity in peak values (~5.5‰) and magnitude of TICE for the Qilinzhai and Belgian sections indicates that the Euro‐asia δ13Ccarbtrends may reflect the changes in global mean ocean δ13CDIC, rather than having been overprinted by local carbon cycling. Integration of conodont biostratigraphy and δ13C stratigraphy provides a powerful tool for stratigraphic correlation. Copyright © 2015 John Wiley & Sons, Ltd.
The Effect of Doping Different Heteroatoms on the Interaction and Adsorption Abilities of Fullerene
Authors: Amiraslanzadeh Saeed
Published: August 2015

Density functional method has been employed to compare the interaction and adsorption abilities of simple and doped fullerenes with various heteroatoms (Al, B, Si, N, P, and S). Three sulfur‐containing molecules (H2S, SO2, and thiophene) were selected to study of their interactions with fullerenes. These interactions will be important in the design of new sensor, adsorption, and elimination of pollutants and chemical reactions. The calculated adsorption energies (Ead) in the gas phase and solvents (water, using the polarized continuum model) showed that all adsorbates have exothermic interaction with all fullerenes. The maximum Ead values were calculated for aluminum‐doped fullerene (AF) and nitrogen‐doped fullerene (NF), and the adsorption energies in solvent are not so different with those in the gas phase. Natural Bond Orbitals (NBO) calculations showed the complexes of AF and then boron‐doped fullerene (BF) have the highest E2 interaction energies, whereas simple fullerene (F) and phosphorus‐doped fullerene (PF) have the least E2 energies. Population analyses showed that doping by heteroatoms bearing extra electrons reduces the energy gap and this decrease is more than the decrease observed from doping by heteroatoms with electron defect. Moreover, the change in the energy gaps of the complexes, obtained from the density of states (DOSs) plots, showed that these structures could be used in sensor devices. All calculated data confirmed the better adsorption of SO2 by fullerenes versus H2S and thiophene and among all fullerenes, AF and then BF and NF are the best adsorbent for these structures.
A New p‐Terphenyl Derivative from the Mushroom Thelephora vialis
Authors: Liu Rui , Wang Ya‐Nan , Xie Bo‐Jun , Pan Qin
Published: August 2015

One novel p‐terphenyl compound, named vialisyl A (1), was isolated from the fruiting bodies of Thelephora vialis, together with six known compounds, ganbajunin B (2), phenylacetic acid (3), a mixture of ganbajunins D (4) and E (5), and vialinins A (6) and B (7). Their structures were established by extensive analysis of spectroscopic data (including 1H‐ and 13C‐NMR, HSQC, HMBC, 2D‐INADEQUATE) as well as by comparison with literature reports.
One‐Pot Four‐Component Synthesis of Thieno[2,3‐d]pyrimidin‐4‐amines via Sequential Gewald/Cyclocondensation Reactions
Authors: Adib Mehdi , Janatian Ghazvini Helia , Soheilizad Mehdi , Saeedi Sara , Tajbakhsh Mahmood , Amanlou Massoud
Published: August 2015

A one‐pot four‐component synthesis of thieno[2,3‐d]pyrimidin‐4‐amines via sequential Gewald/cyclocondensation reactions is described. 2‐Aminothiophene‐3‐carbonitriles obtained from the Gewald reaction between cyclic ketones, malononitrile, and sulfur underwent a condensationcyclization reaction with benzonitriles under solvent‐free conditions to afford the title compounds in excellent yields.
One‐Pot Three‐Component Synthesis ofHantzsch1,4‐Dihydropyridines Promoted by Dimethyl Phosphate Ionic Liquids
Authors: Priede Elina , Zicmanis Andris
Published: August 2015

A one‐pot three‐component reaction of ethyl acetoacetate, AcONH4, and different aldehydes has been successfully performed in the presence of ionic liquids (ILs) possessing a (MeO)2PO$\rm{{_{2}^{-}}}$counterion. The impact of electronic and steric effects of the substituents of aromatic aldehydes, as well as the influence of different anions of ILs on the product yield, have been investigated. The application of dimethyl phosphate ILs in the synthesis ofHantzsch1,4‐dihydropyridines presents a simple method for obtaining structurally diverse products in moderate to high yields without using any additional catalyst.
Synthesis of a Novel Benzocyclotrimer with One Rigid and One Flexible Electron‐Rich Cavity
Authors: Bolzan Alceste , Bortoluzzi Marco , Borsato Giuseppe , Fabbro Chiara , Daştan Arif , De Lucchi Ottorino , Fabris Fabrizio
Published: August 2015

The straightforward synthesis of a novel benzocyclotrimer is herein presented. The syn‐product is characterized by an electron‐rich rigid aromatic cavity and a flexible electron‐rich aromatic pocket. The molecule is a potential scaffold for supramolecular applications.
Stereoselective Total Synthesis of Iso‐Cladospolide B and the 12 Membered‐Macrolactone (6S,12R)‐6‐Hydroxy‐12‐methyloxacyclododecane‐2,5‐dione
Authors: Kumar Pendyala Venkata Arun , Mallula Venkata Satyanarayana , Radha Krishna Palakodety
Published: August 2015

Total syntheses of iso‐cladospolide B (1) and the 12‐membered macrolactone (6S,12R)‐6‐hydroxy‐12‐methyloxacyclododecane‐2,5‐dione (2), a non‐natural product, were achieved from a common intermediate starting from commercially available 1,9‐nonane diol.
Novel and Stereospecific Synthesis of (2S)‐3‐(2,4,5‐Trifluorophenyl)propane‐1,2‐diol from D‐Mannitol
Authors: Aktaş Derya , Fıstıkçı Meryem , Gündoğdu Özlem , Seçen Hasan , Şahin M. Fethi , Altundaş Ramazan , Kara Yunus
Published: August 2015

A stereospecific synthesis of (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol from D‐mannitol has been developed. The reaction of 2,3‐O‐isopropylidene‐D‐glyceraldehyde with 2,4,5‐trifluorophenylmagnesium bromide gave [(4R)‐2,2‐dimethyl‐1,3‐dioxolan‐4‐yl](2,4,5‐trifluorophenyl)methanol in 65% yield as a mixture of diastereoisomers (1 : 1). The Ph3P catalyzed reaction of the latter with C2Cl6 followed by reduction with Pd/C‐catalyzed hydrogenation gave (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol with >99% ee and 65% yield.
Enantiomeric Enrichments via the Self‐Disproportionation of Enantiomers (SDE) by Achiral, Gravity‐Driven Column Chromatography: a Case Study Using N‐(1‐Phenylethyl)acetamide for Optimizing the Enantiomerically Pure Yield and Magnitude of the SDE
Authors: Wzorek Alicja , Sato Azusa , Drabowicz Józef , Soloshonok Vadim A. , Klika Karel D.
Published: August 2015

This work explores the self‐disproportionation of enantiomers (SDE) via achiral, gravity‐driven column chromatography as typically used in laboratory settings for the purpose of enantiomeric enrichment using N‐(1‐phenylethyl)acetamide (PEA) as a case study. The major finding of this work is the very large magnitude of the SDE for PEA across a variety of conditions and broad range of starting ee values, thereby facilitating a simple, reliable, and predictable means of obtaining enantiomerically pure samples. For example, starting with a sample of PEA of ee as low as 28%, a single column run yielded an enantiomerically pure sample (>99.9% ee) from the first fractions and a significantly enantiomerically depleted sample (<17% ee) from the final fractions. An assessment of SDE via achiral, gravity‐driven column chromatography was also rendered with regard to the differing objectives that workers might target – a large magnitude of the SDE, obtaining an optimum sample of desired ee, or preparative‐scale separation of the excess enantiomer. Overall, it can be considered that the SDE phenomenon via achiral, gravity‐driven column chromatography – readily applicable in the usual laboratory settings – is a simple and convenient method for enantiomeric enrichment with a high degree of proficiency. Advantages of SDE via achiral, gravity‐driven column chromatography over conventional fractional recrystallization for the enantiomeric enrichment of amides/amines, and applicable also to many other classes of compounds as well, are discussed.
Synthesis of Benzobis[1,3]oxathiins
Authors: Mayer Axel , Rumpf Norbert , Hillmann Sabine , Meier Herbert
Published: August 2015

Two different synthetic concepts led to the formation of 17, 19, and 29, the first structural isomeric benzobis[1,3]oxathiins. Hetero‐DielsAlder reactions of diethyl mesoxylate 14 and the open valence isomers of the benzobisthietes 12 and 18 yielded the linear benzobis[1,3]oxathiin 17 and its angular isomer 22, respectively. The isomeric angular system 29 could be obtained by a twofold O,S‐acetalization reaction of the dihydroxydisulfanyl compound 27 and acetone (28).
Flavonoids Isolated from Heat‐Processed Epimedium koreanum and Their Anti‐HIV‐1 Activities
Authors: Li Hong‐Mei , Zhou Cheng , Chen Chin‐Ho , Li Rong‐Tao , Lee Kuo‐Hsiung
Published: August 2015

Systematic phytochemical investigation on heat‐processed Epimedium koreanum led to the isolation of 13 flavonoids, including five new prenyl‐flavonol glycosides, koreanosides A–E (1–5, resp.). Their structures were elucidated on the basis of detailed analysis of the 1D‐ and 2D‐NMR spectroscopic data and chemical reactions. Apigenin (11) exhibited moderate anti‐HIV‐1 activity with an EC50 value of 12.8±3.27 μg/ml.
Established methods and new opportunities for pore water stable isotope analysis
Authors: Sprenger Matthias , Herbstritt Barbara , Weiler Markus
Published: August 2015

The vadose zone plays a crucial role in the water cycle for storing water, providing water to vegetation and transporting solutes or degrading contaminants. Earth scientists have long acknowledged the importance of the vadose zone, and numerous methods have been developed to better understand and predict hydrological processes within this ‘critical zone’. For several decades, stable isotopes (18O and 2H) of pore water have been used as environmental tracers to gain insights into vadose zone water movement and other processes. To determine the pore water stable isotopic composition, various sampling procedures have been developed. We present the procedure and the accompanied advantages and drawbacks of each method. We further discuss possible opportunities and limitations regarding the scale of interest and the pore space that is sampled. The methodological review reveals that the choice of sampling method is crucial for the interpretation of pore water stable isotopes in the vadose zone, but a thorough comparison between the different methods is yet missing. Spiking experiments, where water of known isotopic composition is added to oven‐dried soil, have been shown to be questionable, as the extracted water is usually depleted compared with the standard water. A comparative study analysing soil samples with the recently developed direct water vapour equilibration method and the widely used cryogenic extraction shows deviations, which can only be partly explained, but discloses the need for a more thorough experimental comparative study. Especially promising are developments of continuous isotope measurements based on laser‐based spectrometry that will open up new opportunities for analysing pore water isotopes with higher temporal and spatial resolutions, revealing new insights into hydrological processes across various temporal and spatial scales. Copyright © 2015 John Wiley & Sons, Ltd.
Electron transfer pathways in mixed‐valence paracyclophane‐bridged bis‐triarylamine radical cations
Authors: Kaupp Martin , Gückel Simon , Renz Manuel , Klawohn Sascha , Theilacker Kolja , Parthey Matthias , Lambert Christoph
Published: August 2015

A series of paracyclophane (PC) bridged mixed‐valence (MV) bis‐triarylamine radical cations with different ([2.2], [3.3], [4.4]) linkers, with and without additional ethynyl spacers, have been studied by quantum‐chemical calculations (BLYP35‐D3/TZVP/COSMO) of ground‐state structures, thermal electron‐transfer barriers, hyperfine couplings, and lowest‐lying excited states. Such PC‐bridged MV systems are important intra‐molecular model systems for inter‐molecular electron transfer (ET) via π‐stacked aromatics, since they allow enforcement of a more or less well‐defined geometrical arrangement. Closely comparable ET barriers and electronic couplings for all [2.2] and [3.3] bridges are found for these class‐II MV systems, irrespective of the use of pseudo‐para and pseudo‐meta connections. While the latter observation contradicts notions of quantum interference for off‐resonant conduction through molecular wires, it agrees with the less intricate nodal structures of the highest occupied molecular orbitals. The ET in such MV systems may be more closely connected with hole conduction in the resonant regime. Computations on model cations, in which the [2.2] linkers have been truncated, confirm predominant through‐space π‐π electronic coupling. Systems with [4.4] PC bridges exhibit far more structural flexibility and concomitantly weaker electronic interactions between the redox centers. © 2015 Wiley Periodicals, Inc.
Immunogenicity and sustainability of the immune response in Brazilian HIV‐1‐infected individuals vaccinated with inactivated triple influenza vaccine
Authors: Souza Thiago Moreno L. , Santini‐Oliveira Marilia , Martorelli Andressa , Luz Paula M. , Vasconcellos Mauricio T.L. , Giacoia‐Gripp Carmem B.W. , Morgado Mariza , Nunes Estevão P. , Lemos Alberto S. , Ferreira Ana C.G. , Moreira Ronaldo I. , Veloso Valdiléa G. , Siqueira Marilda , Grinsztejn Beatriz , Camacho Luiz A.B.
Published: August 2015

HIV‐infected individuals have a higher risk of serious illnesses following infection by infection with influenza. Although anti‐influenza vaccination is recommended, immunosuppression may limit their response to active immunization. We followed‐up a cohort of HIV‐infected individuals vaccinated against influenza to assess the immunogenicity and sustainability of the immune response to vaccination. Individuals were vaccinated 2011 with inactivated triple influenza vaccine (TIV), and they had received in 2010 the monovalent anti‐A(H1N1)pdm09 vaccine. The sustainability of the immune response to A(H1N1)pdm09 at 12 months after monovalent vaccination fell, both in individuals given two single or two double doses. For these individuals, A(H1N1)pdm09 component from TIV acted as a booster, raising around 40% the number of seroprotected individuals. Almost 70% of the HIV‐infected individuals were already seroprotected to A/H3N2 at baseline. Again, TIV boosted over 90% the seroprotection to A/H3N2. Anti‐A/H3N2 titers dropped by 20% at 6 months after vaccination. Pre‐vaccination seroprotection rate to influenza B (victoria lineage) was the lowest among those tested, seroconversion rates were higher after vaccination. Seroconversion/protection after TIV vaccination did not differ significantly across categories of clinical and demographic variables. Anti‐influenza responses in Brazilian HIV‐infected individuals reflected both the previous history of virus circulation in Brazil and vaccination. J. Med. Virol. 88:426–436, 2016. © 2015 Wiley Periodicals, Inc.
Trends in mean and extreme precipitation in the Mount Kenya region from observations and reanalyses
Authors: Schmocker J. , Liniger H. P. , Ngeru J. N. , Brugnara Y. , Auchmann R. , Brönnimann S.
Published: August 2015

Land and water management in semi‐arid regions requires detailed information on precipitation distribution, including extremes, and changes therein. Such information is often lacking. This paper describes statistics of mean and extreme precipitation in a unique data set from the Mount Kenya region, encompassing around 50 stations with at least 30 years of data. We describe the data set, including quality control procedures and statistical break detection. Trends in mean precipitation and extreme indices calculated from these data for individual rainy seasons are compared with corresponding trends in reanalysis products. From 1979 to 2011, mean precipitation decreased at 75% of the stations during the ‘long rains’ (March to May) and increased at 70% of the stations during the ‘short rains’ (October to December). Corresponding trends are found in the number of heavy precipitation days, and maximum of consecutive 5‐day precipitation. Conversely, an increase in consecutive dry days within both main rainy seasons is found. However, trends are only statistically significant in very few cases. Reanalysis data sets agree with observations with respect to interannual variability, while correlations are considerably lower for monthly deviations (ratios) from the mean annual cycle. While some products well reproduce the rainfall climatology and some the spatial trend pattern, no product reproduces both.
Optical spectroscopic determination of human meniscus composition
Authors: Ala‐Myllymäki Juho , Honkanen Juuso T.J. , Töyräs Juha , Afara Isaac O.
Published: August 2015

This study investigates the correlation between the composition of human meniscus and its absorption spectrum in the visible (VIS) and near infrared (NIR) spectral range. Meniscus samples (n = 24) were obtained from nonarthritic knees of human cadavers with no history of joint diseases. Specimens (n = 72) were obtained from three distinct sections of the meniscus, namely; anterior, center, posterior. Absorption spectra were acquired from each specimen in the VIS and NIR spectral range (400–1,100 nm). Following spectroscopic probing, the specimens were subjected to biochemical analyses to determine the matrix composition, that is water, hydroxyproline, and uronic acid contents. Multivariate analytical techniques, including principal component analysis (PCA) and partial least squares (PLS) regression, were then used to investigate the correlation between the matrix composition and it spectral response. Our results indicate that the optical absorption of meniscus matrix is related to its composition, and this relationship is optimal in the NIR spectral range (750–1,100 nm). High correlations (R2uronic = 86.9%, R2water = 83.8%, R2hydroxyproline = 81.7%, p < 0.0001) were obtained between the spectral predicted and measured meniscus composition, thus suggesting that spectral data in the NIR range can be utilized for estimating the matrix composition of human meniscus. In conclusion, optical spectroscopy, particularly in the NIR spectral range, is a potential method for evaluating the composition of human meniscus. This presents a promising technique for rapid and nondestructive evaluation of meniscus integrity in real‐time during arthroscopic surgery. © 2015 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 34:270–278, 2016.
Sustained release of bioactive protein from a lyophilized tissue‐engineered construct promotes the osteogenic potential of mesenchymal stem cells
Authors: Deng Moyuan , Chang Zhengqi , Hou Tianyong , Dong Shiwu , Pang Hao , Li Zhiqiang , Luo Fei , Xing Junchao , Yu Bo , Yi Shaoxuan , Xu Jianzhong
Published: August 2015

Tissue‐engineered constructs (TECs) seeded with mesenchymal stem cells (MSCs) represent a therapy for large bone defects. However, massive cell death in TECs in the early postimplantation period prompted us to investigate the osteoinductive mechanism of TECs. Previous studies demonstrated that stem cell extracts retained equivalent levels of bioactive proteins and exhibited an osteoinductive nature similar to that of intact cells. These data led us to hypothesize that despite the massive cell death in TECs, devitalized MSC‐derived proteins remain on the scaffolds and are released to improve cell function. Here, TECs were prepared using demineralized bone matrix seeded with human umbilical cord Wharton's jelly‐derived MSCs (hWJMSCs), and the cells seeded in TECs were devitalized by lyophilizing the TECs. Scanning electron microscopy, BCA protein assays, quantitative cytokine array analysis and immunofluorescent staining indicated that approximately 3 mg/cm3 of total protein and 49 types of cytokines derived from hWJMSCs were preserved in the lyophilized TECs (LTECs). The sustainable release of total protein and cytokines from LTECs lasted for more than 2 weeks. The released protein improved the osteogenic behavior of and gene expression in MSCs. Furthermore, the lyophilized hWJMSC‐derived proteins had immunoregulatory properties similar to those of live MSCs in mixed lymphocyte reactions. Collectively, we present a novel perspective on the osteoinductive mechanism of TECs and introduce LTECs as new systems for delivering multiple cytokines to enhance MSC behavior. © 2015 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 34:386–394, 2016.
Improving access and timeliness of care for veterans with head and neck squamous cell carcinoma: A multidisciplinary team's approach
Authors: Patil Reena Dhanda , Meinzen‐Derr Jareen K. , Hendricks Brian L. , Patil Yash J.
Published: August 2015

Objectives/Hypothesis

With the prevalence of head and neck squamous cell carcinoma (HNSCC) nearly twice as high in veterans (6%) than general populations (3%), the noted problems of long waits and access to care in United States Veterans Affairs (VA) hospitals across the country are pressing. We examined primary outcome measures of timeliness and access to care for our patients with HNSCC assessing a multidisciplinary team approach at our VA hospital.

Study Design

Retrospective chart review.

Methods

Our patients newly diagnosed with HNSCC were identified from two 24‐month periods: diagnosis before (group 1, 2005–2006) and after (group 2, 2008–2009) implementing our multidisciplinary team in 2007. No significant differences in age (P = .13) or disease stage (P = .18) occurred between groups. Primary and secondary outcomes (i.e., treatment modality, imaging, completion of treatment, survival) were compared.

Results

Timeliness to care improved for all measures. Improvement was significant for times from consult placed to seen in clinic (27.5–16.5 days; P < 0.0001) and from positive biopsy reported to date of initiating definitive treatment (35–27 days; P = 0.04). Pretreatment consults to various services represented by the multidisciplinary team increased from one to four (P < 0.0001). Two‐year mortality was approximately the same between group 1 (33%) and group 2 (36%) (P = 0.035). Five‐year mortality was slightly better in group 2 (50%) versus group 1 (61%), although not statistically significant.

Conclusion

Our veteran population with HNSCC had improved timeliness and access to care with our multidisciplinary approach.

Level of Evidence

4. Laryngoscope, 126:627–631, 2016