bluuebunny/crossref_metadata_2025 huggingface dataset:
Molecular and Polymeric Uranyl and Thorium Complexes with Sulfonate‐Containing Ligands
Authors: Thuéry Pierre
Published: November 2013

Six uranyl and one thorium(IV) cation complexes with ligands involving either only sulfonate or both sulfonate and carboxylate groups as complexing sites were obtained, mainly under hydrothermal conditions, and their crystal structures were determined. The uranyl ion complex with the 2‐sulfobenzoate (2‐SB2–) anion synthesized in the presence of pyridine, [pyH]4[(UO2)2(2‐SB)2O]2·4H2O (1), is a molecular, tetranuclear complex in which 2‐SB2– is chelating through its two functional groups, while [Th(2‐SB)2(H2O)3]·2H2O (2) is a 1D polymer with monodentate sulfonate and bridging bidentate carboxylate groups. Complex [(UO2)3K(4‐SB)O(OH)3(H2O)1.5]·0.5H2O (3), with the 4‐sulfobenzoate ligand, crystallizes as a 3D framework in which uranyl oxo/hydroxo 1D subunits are connected to one another by 4‐SB2– and potassium cation bridges, the latter being involved in as much as five bonds with uranyl oxo groups (“cation–cation” bonds). Complex [UO2(5‐SSH2)(H2O)3]2·2(5‐SSH2)·3H2O (4), with 5‐sulfosalicylic acid (5‐SSH3), is a dinuclear species in which the ligand is only coordinated through its bridging bidentate sulfonate group, an unusual occurrence. 5‐Sulfosalicylic acid undergoes partial desulfonation and carboxylation under hydrothermal conditions, yielding the heterometallic, tetranuclear complex [UO2Ni(5‐SHIPH)(4‐HIPH2)(bipy)2(H2O)]2·(4‐HIPH3) (5), 5‐sulfonato‐2‐hydroxyisophthalic acid (5‐SHIPH4) and 4‐hydroxyisophthalic acid (4‐HIPH3) being generated in situ. The all‐sulfonate ligand 1,2‐ethanedisulfonate (EDS2–) acts as a divergent linker in both [UO2(EDS)(H2O)3] (6) and [(UO2)2(EDS)(OH)2(phen)2]·4H2O (7). 1D polymers are formed in both cases, the doubly monodentate EDS2– ligand bridging isolated uranyl ions in 6 or hydroxo‐bridged uranyl dimers in 7. Sulfonate coordination to the 5f cation is present in all these complexes but 5, even in the absence of synergistic effects exerted by the stronger carboxylate ligating groups, and the variety of structures obtained in this as well as in previous work demonstrates that, together with the more investigated phosphonates, sulfonates are anions of great potential for the synthesis of actinide–organic coordination polymers and frameworks.
Formation of 1,3‐Diphosphacyclobutadiene Complexes from Phosphaalkynes and Their Coordination Behavior
Authors: Rummel Eva‐Maria , Eckhardt Maria , Bodensteiner Michael , Peresypkina Eugenia V. , Kremer Werner , Gröger Christian , Scheer Manfred
Published: November 2013

By using [(Cp″′Co)2tol] (Cp″′ = η5‐C5H2tBu3, tol = toluene), a new synthesis of the 1,3‐diphosphete complexes [Cp″′Co(η4‐P2C2tBu2)] (1a) and [Cp″′Co(η4‐P2C2iPr2)] (1b) was found, and their reactions with the Lewis acids W(CO)4 and CuI halides were investigated. The reaction of 1b with W(CO)4(nbd) (nbd = norbornadiene) leads to the complex [(Cp″′Co)(μ,η4:1‐{PCiPr}2)]2W(CO)4 (2) with the two diphosphete complexes 1b coordinated trans to a central W(CO)4 moiety. The reactions of 1a with CuI halides result in different products depending on the stoichiometry. In a 1:1 ratio, the dimeric compounds 3a–c [(Cp″′Co)(μ,η4:1‐{PCtBu}2)Cu(μ‐X)]2 (3a: X = Cl; 3b: X = Br, 3c: X = I) were isolated, whereas an excess of CuX gave the two‐dimensional polymers [({Cp″′Co}{μ3,η4:1:1‐(PCtBu)2})2(Cu{μ3‐X})4]n (6a: X = Cl, 6b: X = Br, 6c: X = I). From the reaction of 1a and 1b with CuBr and CuI in a 1:2 or 2:3 ratio, the one‐dimensional polymers [({Cp″′Co}{μ3,η4:1:1‐(PCR)2})({Cp″′Co}{μ,η4:1‐(PCR)2})(Cu{μ3‐X})4]n (4a: X = Br, R = iPr, 4b: X = I, R = iPr, 4c: X = I, R = tBu) are formed. From the reaction of 1a with CuI, a second product, [({Cp″′Co}{μ3,η4:1:1‐(PCtBu)2})(Cu{μ3‐I})4(MeCN)2]n (5), was isolated by using CH3CN for crystallization. The products were comprehensively characterized by spectroscopic methods, X‐ray crystallography, and 31P magic angle spinning (MAS) NMR spectroscopy.
Improved Yields for the Palladium‐Mediated 11C‐Carbonylation Reaction Using Microwave Technology
Authors: Dahl Kenneth , Schou Magnus , Rahman Obaidur , Halldin Christer
Published: November 2013

Microwave heating technology was applied for the palladium‐mediated 11C‐carbonylation of aryl halides and triflates at ambient pressure using xantphos as supporting ligand. Improved yields were observed for the 11C‐aminocarbonylation of electron‐deficient aryl halides in comparison to thermal heating and the approach even allowed the use of an aryl chloride as substrate. The scope of this reaction was further extended to 11C‐labeled aryl acid and two 11C‐labeled aryl esters.
Investigations on the Operation of Stereochemical Drift in the Wittig Reaction by NMR and Variable‐Temperature NMR Spectroscopy of Oxaphosphetane Intermediates and Their Quench Products
Authors: Byrne Peter A. , Muldoon Jimmy , Ortin Yannick , Müller‐Bunz Helge , Gilheany Declan G.
Published: November 2013

Within the currently accepted mechanism of the Li‐salt‐free Wittig reaction, the phenomenon of stereochemical drift remains the one remaining “loose end” in an otherwise internally consistent explanation of a large body of diverse observations. The term describes the nonstereospecific decomposition of the oxaphosphetane (OPA) intermediate in reactions of certain alkylides with certain aldehydes. In this paper, it is shown that the previous examples in which drift occurs are not merely isolated aberrations from the observed norm, but rather that there is a general phenomenon in reactions of ethylides with benzaldehydes. Variable‐temperature NMR (VTNMR) spectroscopy was used to establish that the amount and diastereomeric ratio of the OPA intermediates do not change below a certain temperature. At and above the temperature at which OPA decomposition to alkene and phosphine oxide begins to occur, the alkene shows a different diastereomeric ratio to the OPA, which indicates the occurrence of stereochemical drift. In one example, owing to an apparent remarkable coincidence of rates, the diastereomeric ratio of the OPA does not change above the decomposition temperature, even though stereochemical drift occurs in the formation of the alkene product. An alternative mechanism for drift involving its catalysis by aldehyde was not confirmed. Drift was also shown not to occur in similar Wittig reactions of structurally related longer‐chain alkylides by stereospecific decomposition of OPA intermediates generated from β‐hydroxyphosphonium salts (β‐HPSs). The extremely useful (and generally applicable) NMR techniques, 1H–31P HMBC and selective 1H{31P}, which we have utilised to establish kinetic diastereomeric ratios, are described in full for the first time. Details of the determination of the relative stereochemistry of two β‐HPSs (derived from acid quenching of OPAs) by X‐ray crystallography are also given.
Enantioselective Organocatalytic Synthesis of α‐Cyclopropylphosphonates through a Domino Michael Addition/Intramolecular Alkylation Reaction
Authors: Faísca Phillips Ana Maria , Barros Maria Teresa
Published: November 2013

An organocatalytic domino reaction consisting of Michael addition/intramolecular alkylation between α,β‐unsaturated aldehydes and bromophosphonoacetates was developed. Highly functionalised cyclopropylphosphonates containing three chiral centres, one of them quaternary, were obtained with good diastereoselectivities of up to 83:17 and very high enantioselectivities of up to 99 %.
Silver(I)‐Mediated Dual Cleavage of C–C and C–O Bonds in the Reaction of Diarylmethylenecyclopropanes with Tetrahydrofuran: Synthesis of 4‐(3‐Halobut‐3‐enyloxy)butyl 2,2,2‐Trifluoroacetate Derivatives
Authors: Chen Gen‐Qiang , Tang Xiang‐Ying , Shi Min
Published: November 2013

The reaction of methylenecyclopropanes (MCPs) with tetrahydrofuran (THF) proceed smoothly in the presence of AgOC(O)CF3 and electrophilic halogenation reagents to give the corresponding 4‐(3‐halobut‐3‐enyloxy)butyl 2,2,2‐trifluoroacetate derivatives in moderate yields through dual cleavage of C–C and C–O bonds under mild conditions.
A Convenient Route for the Synthesis of 3‐Deazaspongosine
Authors: Bande Omprakash , Herdewijn Piet
Published: November 2013

The first chemical synthesis of the 3‐deazaspongosine nucleoside is described, starting from commercially available 4‐amino‐2,6‐dichloropyridine. The key step is the introduction of required functional groups at the 2 and 6 positions of the 4‐amino‐3‐nitropyridine without any conflict in the synthesis of nucleobase. Regioselective nucleophilic substitution with allyl alkoxide at the 2 position of 4‐amino‐2,6‐dimethoxypyridine, followed by sequential deallylation and chlorination led to the desired 2‐chloro derivative. Ring closure of the 3,4‐diaminopyridine and stereoselective glycosylation of the imidazo[4,5‐c]pyridine with tetraacetate‐protected ribofuranose gave only the N9‐β‐isomer. A final nucleophilic displacement of the 6‐chloride by hydrazine followed by reduction with Raney Nickel gave the desired 3‐deazaspongosine.
Synthesis of GABOB and GABOB‐Based Chiral Units Possessing Distinct Protecting Groups
Authors: Ivšić Trpimir , Dokli Irena , Rimac Ana , Hameršak Zdenko
Published: November 2013

In addition to the varied biological activity of GABOB (4‐amino‐3‐hydroxybutanoic acid), the structure of its protected derivatives makes them interesting chiral intermediates for the synthesis of more complex compounds. A stereoselective route to GABOB derivatives with three different protecting groups is presented, using anhydride desymmetrization as a chirality‐inducing step. Selective removal of the protecting groups gave compounds with a free carboxylic acid or hydroxy group. Removal of all of the protecting groups allowed GABOB to be isolated in good yield and with excellent ee.
Fused Azacalix[4]arenes
Authors: Haddoub Rose , Touil Mounia , Chen Zhongrui , Raimundo Jean‐Manuel , Marsal Philippe , Elhabiri Mourad , Siri Olivier
Published: November 2013

The synthesis of unprecedented fused azacalixarenes (dimers and trimer) through successive nucleophilic aromatic substitutions is described. Absorption spectrophotometric and theoretical studies demonstrated that these oligomers share common phenyl moieties that enable conjugation of the whole π‐system and a multiconcave geometry with aligned cavities because of the high flexibility of these macrocycles.
Lab‐on‐a‐Chip Sensor with Evaporated Bismuth Film Electrode for Anodic Stripping Voltammetry of Zinc
Authors: Kang Wenjing , Pei Xing , Yue Wei , Bange Adam , Heineman William R. , Papautsky Ian
Published: November 2013

In this work, we report on the development of a lab‐on‐a‐chip electrochemical sensor that uses an evaporated bismuth electrode to detect zinc using square wave anodic stripping voltammetry. The microscale electrochemical cell consists of a bismuth working electrode, an integrated silver/silver chloride reference electrode, and a gold auxiliary electrode. The sensor exhibits a linear response in 0.1 M acetate buffer at pH 6 with zinc concentrations in the 1–30 μM range and a calculated detection limit of 60 nM. The sensor successfully detected zinc in a bovine serum extract and the results were corfirmed by independent AAS measurements. Our results demonstrate the advantageous qualities of this lab‐on‐a‐chip electrochemical sensor for clinical applications, which include small sample volume (µL scale), reduced cost, short response time and high accuracy at low concentrations of analyte.
Voltammetry of Immobilized Particles of Cannabinoids
Authors: Novak Ivana , Mlakar Marina , Komorsky‐Lovrić Šebojka
Published: November 2013

A new electrochemical method for the detection of cannabinoids in food products is proposed. The method is based on the voltammetry of microparticles at a paraffin‐impregnated graphite electrode. In square‐wave voltammetry, in 0.1 M KNO3 at pH 7, the responses of delta‐9‐tetrahydrocannabinol, cannabinol and cannabidiol consist of a single peak with the maximum at 0.55 V±0.01 V. This peak is ascribed to the electrooxidation of the phenol group to phenoxy radical. In microparticles of hemp and marijuana cannabinoids can be detected in pure drug as well as in the mixture with foreign insoluble powders.
Fe3O4 Microspheres and Graphene Oxide Encapsulated with Chitosan: A New Platform for Sensitive Determination of Hydroquinone and Catechol
Authors: Lai Ting , Cai Weihua , Du Haijun , Ye Jianshan
Published: November 2013

A novel sensor for sensitive determination of hydroquinone (HQ) and catechol (CC) was proposed using a Fe3O4 microspheres‐graphene oxide (Fe3O4‐GO) composites modified glassy carbon electrode (GCE) which was further encapsulated with chitosan (Chit‐Fe3O4‐GO/GCE). The excellent electrocatalytic performance is probably related to the strong synergistic effect of the composites. The proposed sensor shows a linear response for HQ and CC in wide concentration ranges from 1.5 to 150 µM and 1 to 410 µM, with detection limits (S/N=3) of 20 and 250 nM, respectively. Additionally, the sensor exhibits good selectivity and stability in tap water samples.
Pilot spark energy in the cone calorimeter: a source of measurement uncertainties
Authors: Ochoterena Raúl , Försth Michael
Published: November 2013

This work presents measurements meant to study the influence of the spark energy on the time to ignition of a given material in the cone calorimeter. For this purpose, square slabs of particle board were tested under two radiation intensities until ignition occurred using two spark energies for each intensity level. Results show that increasing the spark energy leads to a reduction in the ignition time regardless of the radiation intensity. However, the influence of the spark energy on the time to ignition is, in absolute numbers, larger for the low radiation intensity case than for the high radiation intensity case. Nonetheless, the proportional difference is nearly 10% for both levels of heat radiation. Results from this work confirm that there is an influence of the spark energy on the time to ignition of a given material suggesting that a narrower and more specific definition of the ignition circuits allowed in the cone calorimeter would be highly beneficial for ensuring repeatable results among laboratories. Copyright © 2013 John Wiley & Sons, Ltd.
Genetic Prediction of Quantitative Lipid Traits: Comparing Shrinkage Models to Gene Scores
Authors: Warren Helen , Casas Juan‐Pablo , Hingorani Aroon , Dudbridge Frank , Whittaker John
Published: November 2013

Accurate genetic prediction of quantitative traits related to complex disease risk would have potential clinical impact, so investigation of statistical methodology to improve predictive performance is important. We compare a simple approach of polygenic scores using top ranking single nucleotide polymorphisms (SNPs) to a set of shrinkage models, namely Ridge Regression, Lasso and Hyper‐Lasso. These penalised regression methods analyse all genotyped SNPs simultaneously, potentially including much larger sets of SNPs in the models, not only those with the smallestPvalues. We compare the accuracy of these models for predicting low‐density lipoprotein (LDL) and high‐density lipoprotein (HDL) cholesterol, two lipid traits of clinical relevance, in the Whitehall II and British Women's Health and Heart Study cohorts, using SNPs from the HumanCVD BeadChip. For gene scores, the most accurate predictions arise from multivariate weighted scores and include only a small number of SNPs, identified as top hits by the HumanCVD BeadChip. Furthermore, there was little benefit from including external results from published sets of SNPs. We found that shrinkage approaches rarely improved significantly on gene score results. Genetic predictive performance is trait specific, depending on the heritability and genetic architecture of the trait, and is limited by the training data sample size. Our results for lipid traits suggest no current benefit of more complex methods over existing gene score methods. Instead, the most important choice for the prediction model is the number of SNPs and selection of the most predictive SNPs to include. However further comparisons, in larger samples and for other phenotypes, would still be of interest.
The A1 adenosine receptor as a new player in microglia physiology
Authors: Luongo L. , Guida F. , Imperatore R. , Napolitano F. , Gatta L. , Cristino L. , Giordano C. , Siniscalco D. , Di Marzo V. , Bellini G. , Petrelli R. , Cappellacci L. , Usiello A. , de Novellis V. , Rossi F. , Maione S.
Published: November 2013

The purinergic system is highly involved in the regulation of microglial physiological processes. In addition to the accepted roles for the P2X4,7 and P2Y12 receptors activated by adenosine triphosphate (ATP) and adenosine diphosphate, respectively, recent evidence suggests a role for the adenosine A2A receptor in microglial cytoskeletal rearrangements. However, the expression and function of adenosine A1 receptor (A1AR) in microglia is still unclear. Several reports have demonstrated possible expression of A1AR in microglia, but a new study has refuted such evidence. In this study, we investigated the presence and function of A1AR in microglia using biomolecular techniques, live microscopy, live calcium imaging, and in vivo electrophysiological approaches. The aim of this study was to clarify the expression of A1AR in microglia and to highlight its possible roles. We found that microglia express A1AR and that it is highly upregulated upon ATP treatment. Moreover, we observed that selective stimulation of A1AR inhibits the morphological activation of microglia, possibly by suppressing the Ca2+ influx induced by ATP treatment. Finally, we recorded the spontaneous and evoked activity of spinal nociceptive‐specific neuron before and after application of resting or ATP‐treated microglia, with or without preincubation with a selective A1AR agonist. We found that the microglial cells, pretreated with the A1AR agonist, exhibit lower capability to facilitate the nociceptive neurons, as compared with the cells treated with ATP alone. GLIA 2014;62:122–132
Microglial TNF‐α mediates enhancement of dopaminergic degeneration by brain angiotensin
Authors: Borrajo Ana , Rodriguez‐Perez Ana I. , Diaz‐Ruiz Carmen , Guerra Maria J. , Labandeira‐Garcia Jose L.
Published: November 2013

In vitro and in vivo models of Parkinson's disease were used to investigate whether TNF‐α plays a major role in the enhancement of the microglial response and dopaminergic degeneration induced by brain angiotensin hyperactivity. Treatment of primary mesencephalic cultures with low doses of the neurotoxin MPP+ induced a significant loss of dopaminergic neurons, which was enhanced by cotreatment with angiotensin II and inhibited by TNF‐α inhibitors. Treatment of primary cultures with angiotensin induced a marked increase in levels of TNF‐α, which was inhibited by treatment with angiotensin type‐1‐receptor antagonists, NADPH‐oxidase inhibitors and NFK‐β inhibitors. However, TNF‐α levels were not significantly affected by treatment with angiotensin in the absence of microglia. The microglial origin of the angiotensin‐induced increase in TNF‐α levels was confirmed using dopaminergic (MES 23.5) and microglial (N9) cell lines. Inhibition of the microglial Rho‐kinase activity also blocked the AII‐induced increase in TNF‐α levels. Treatment of the dopaminergic cell line with TNF‐α revealed that NFK‐β activation mediates the deleterious effect of microglial TNF‐α on dopaminergic neurons. Treatment of mice with MPTP also induced significant increases in striatal and nigral TNF‐α levels, which were inhibited by angiotensin type‐1‐receptor antagonists or NFK‐β inhibitors. The present results show that microglial TNF‐α plays a major role in angiotensin‐induced dopaminergic cell death and that the microglial release of TNF‐α is mediated by activation of angiotensin type‐1 receptors, NADPH‐oxidase, Rho‐kinase and NFK‐β. GLIA 2014;62:145–157
Evaluation of cytology and visual triage of human papillomavirus‐positive women in cervical cancer prevention in India
Authors: Muwonge Richard , Wesley Ramani S. , Nene Bhagwan M. , Shastri Surendra S. , Jayant Kasturi , Malvi Sylla G. , Thara Somanathan , Sankaranarayanan Rengaswamy
Published: November 2013

Although virtually all cervical cancers and most cervical intraepithelial neoplasia (CIN) are caused by persistent human papillomavirus (HPV) infection, only a small proportion of HPV‐positive women have or will develop CIN. Triaging HPV‐positive women has been suggested to reduce the false‐positive rate and proportion of women referred for CIN confirmation and/or treatment. In two cross‐sectional studies and one randomized trial in India, we evaluated the impact of using cytology or visual inspection with acetic acid (VIA) to triage HPV‐positive women on the proportion of women who would be referred for CIN confirmation and on the detection rates of high‐grade CIN. We present the numbers of HPV test‐positive women found and the CIN detected among them. We further assess the proportions that would be referred for CIN confirmation with colposcopy/biopsy and CIN that would be detected if cytology triage or VIA triage were used. Using cytology triage at atypical squamous cells of undetermined significance threshold or VIA triage reduced referrals for colposcopy by about 62% and 59%, respectively (p‐value = 0.012), but missed around 16% and 18%, respectively, of the high‐grade CIN (p‐value = 0.539) indicating similar performance of both triaging approaches. The choice of a triage test in different low‐ and middle‐income countries (LMIC) would depend on the availability and affordability in the particular setting. Cytology triage may be considered in settings where adequate infrastructure exists, whereas VIA triage may be suitable in settings with limited or no cytology infrastructure.
Self‐Optimizing Reactor Systems: Algorithms, On‐line Analytics, Setups, and Strategies for Accelerating Continuous Flow Process Optimization
Authors: Fabry David C. , Sugiono Erli , Rueping Magnus
Published: November 2013

This review provides an overview of recent developments in the area of continuous flow process optimization by employing self‐optimizing reactor systems. Although only few reactor concepts have been realized to date, impressive progress has been made, which now allows fully automated reaction optimization without the need of human interactions.
Ecological momentary assessment for chronic pain in fibromyalgia using a smartphone: A randomized crossover study
Authors: Garcia‐Palacios A. , Herrero R. , Belmonte M.A. , Castilla D. , Guixeres J. , Molinari G. , Baños R.M. , Botella C.
Published: November 2013

Background

Daily diaries are a useful way of measuring fluctuations in pain‐related symptoms. However, traditional diaries do not assure the gathering of data in real time, not solving the problem of retrospective assessment. Ecological momentary assessment (EMA) by means of electronic diaries helps to improve repeated assessment. However, it is important to test its feasibility in specific populations in order to reach a wider number of people who could benefit from these procedures.

Methods

The present study compares the compliance and acceptability of an electronic diary running on a smartphone using a crossover design for a sample with a specific pain condition, fibromyalgia and low familiarity with technology. Forty‐seven participants were randomly assigned to one of two conditions: (1) paper diary – smartphone diary and (2) smartphone diary – paper diary, using each assessment method for 1 week.

Results

The findings of this study showed that the smartphone diary made it possible to gather more accurate and complete ratings. Besides, this method was well accepted by a sample of patients with fibromyalgia referred by a public hospital, with an important proportion of participants with low level of education and low familiarity with technology.

Conclusions

The findings of this study support the use of smartphones for EMA even in specific populations with a specific pain condition, fibromyalgia and with low familiarity with technology. These methods could help clinicians and researchers to gather more accurate ratings of relevant pain‐related variables even in populations with low familiarity with technology.
Current status and future trends for disposable technology in the biopharmaceutical industry
Authors: Allison Nigel , Richards Jackie
Published: November 2013

Single use technology (SUT) is in widespread use throughout the biopharmaceutical industry where it is replacing traditional stainless steel plant particularly for the manufacture of small volume, high value products. The key drivers for SUT uptake include reduction of regulatory risk, lower capital and energy costs and increased facility flexibility. Disposable technology is now well established for cell culture, liquid handling and storage but its application to some downstream operations is proving more intractable. Single‐use chromatography resins are generally uneconomic at process scale and there are limitations on large‐scale tangential flow filtration capacities. The development of disposable sensor technology is lagging behind that of bioreactors and capacities for microbial culture are presently limited to 2000 litres. Concerns regarding compatibility of equipment from different suppliers and extractable and leachable testing are being addressed but continue to influence uptake of SUT by traditional manufacturers. Complete ‘plug and play’ disposable process trains, however, are becoming increasingly available and are being embraced by Contract Manufacturing Organisations (CMOs) with multiproduct facilities. © 2013 Society of Chemical Industry
A Facile Method for the Synthesis of Aroyl Pyrazoles from Functionalized Ketene Dithioacetals
Authors: Sreedevi N. K. , Mathews A. , Devaky K. S. , Anabha E. R.
Published: November 2013

On treating with ammonium acetate in DMSO aroyl formyl ketene dithioacetals were transformed into valuable intermediates 3‐amino‐2‐aroyl‐3‐(methylsulfanyl)‐2‐propenals, which could be explored for the synthesis of aroyl aminopyrazoles.
miR‐252 of the Asian tiger mosquito Aedes albopictus regulates dengue virus replication by suppressing the expression of the dengue virus envelope protein
Authors: Yan Hui , Zhou Yanhe , Liu Yanxia , Deng Yuhua , Puthiyakunnon Santhosh , Chen Xiaoguang
Published: November 2013

The Asian tiger mosquito, Aedes albopictus is a major vector of dengue in mainland China. Dengue epidemics have spread from the southern coastal regions to the relatively northern and western regions since 1990s. Dengue has become an emerging public health problem in the southern coastal regions. microRNAs (miRNAs) are short non‐coding RNAs that regulate gene expression at the post‐transcriptional level. A highly abundant miRNA, miR‐252, was induced more than threefold after dengue virus serotype 2 (DENV‐2) infection in the Ae. albopictus C6/36 cell line. Transfection with miR‐252 inhibitor resulted in the increase of DENV‐2 RNA copies and the up‐regulation of DENV‐2 envelop protein (E protein) expression, whereas over expression of miR‐252 with its mimic decreased DENV RNA copies and the down‐regulation of E protein expression. MiR‐252 mimic reduced luciferase activity of a luciferase reporter that contained the predicted miR‐252 target on the DENV‐2 envelope gene sequence. The present results indicated that the miR‐252 of Ae. albopictus could regulate the gene expression of DENV‐2 E protein and may act as a cellular antiviral regulator in Ae. albopictus. J. Med. Virol. 86:1428–1436, 2014. © 2013 Wiley Periodicals, Inc.
Comparison of EBV DNA viral load in whole blood, plasma, B‐cells and B‐cell culture supernatant
Authors: Ouedraogo David Eric , Bollore Karine , Viljoen Johannes , Foulongne Vincent , Reynes Jacques , Cartron Guillaume , Vendrell Jean‐Pierre , Van de Perre Philippe , Tuaillon Edouard
Published: November 2013

Epstein–Barr virus (EBV) genome quantitation in whole blood is used widely for therapeutic monitoring of EBV‐associated disorders in immunosuppressed individuals and in patients with EBV‐associated lymphoma. However, the most appropriate biological material to be used for EBV DNA quantitation remains a subject of debate. This study compare the detection rate and levels of EBV DNA from whole blood, plasma, enriched B‐cells, and B‐cell short‐term culture supernatant using quantitative real‐time PCR. Samples were collected from 33 subjects with either HIV infection or B‐cell lymphoma. Overall, EBV DNA was detected in 100% of enriched B‐cell samples, in 82% of B‐cell culture supernatants, in 57% of plasma, and 42% of whole blood samples. A significant correlation for EBV viral load was found between enriched B‐cell and B‐cell culture supernatant material (ρ = 0.92; P < 0.0001), but no significant correlation existed between EBV DNA levels in whole blood and enriched B‐cells (ρ = −0.02; P = 0.89), whole blood and plasma (ρ = 0.24; P = 0.24), or enriched B‐cells and plasma (ρ = 0.08; P = 0.77). Testing of enriched B‐cells appeared to be the most sensitive method for detection of EBV DNA as well as for exploration of the cellular reservoir. Quantitation of EBV DNA in plasma and B‐cell culture supernatant may be of interest to assess EBV reactivation dynamics and response to treatment as well as to decipher EBV host–pathogen interactions in various clinical scenarios. J. Med. Virol. 86:851–856, 2014. © 2013 Wiley Periodicals, Inc.
Oxidative damage and amyloid‐β metabolism in brain regions of the longest‐lived rodents
Authors: Edrey Yael H. , Oddo Salvatore , Cornelius Carolin , Caccamo Antonella , Calabrese Vittorio , Buffenstein Rochelle
Published: November 2013

Naked mole rats (NMRs) are the longest‐lived rodents, with young individuals having high levels of Aβ in their brains. The purpose of this study was twofold: to assess the distribution of Aβ in key regions of NMR brains (cortex, hippocampus, cerebellum) and to understand whether the accumulation of Aβ is due to enhanced production or decreased degradation. Recent evidence indicates that lipid peroxides directly participate in induction of cytoprotective proteins, such as heat shock proteins (Hsps), which play a central role in the cellular mechanisms of stress tolerance. Amyloid precursor protein processing, lipid peroxidation, Hsps, redox status, and protein degradation processes were therefore assessed in key NMR brain regions. NMR brains had high levels of lipid peroxidation compared with mice, and the NMR hippocampus had the highest levels of the most toxic moiety of Aβ (soluble Aβ1–42). This was due not to increased Aβ production but rather to low antioxidant potential, which was associated with low induction of Hsp70 and heme oxygenase‐1 as well as low ubiquitin‐proteasome activity. NMRs may therefore serve as natural models for understanding the relationship between oxidative stress and Aβ levels and its effects on the brain. © 2013 Wiley Periodicals, Inc.
Influence of biochemical composition on endplate cartilage tensile properties in the human lumbar spine
Authors: Fields Aaron J. , Rodriguez David , Gary Kaitlyn N. , Liebenberg Ellen C. , Lotz Jeffrey C.
Published: November 2013

Endplate cartilage integrity is critical to spine health and is presumably impaired by deterioration in biochemical composition. Yet, quantitative relationships between endplate biochemical composition and biomechanical properties are unavailable. Using endplate cartilage harvested from human lumbar spines (six donors, ages 51–67 years) we showed that endplate biochemical composition has a significant influence on its equilibrium tensile properties and that the presence of endplate damage associates with a diminished composition–function relationship. We found that the equilibrium tensile modulus (5.9 ± 5.7 MPa) correlated significantly with collagen content (559 ± 147 µg/mg dry weight, r2 = 0.35) and with the collagen/GAG ratio (6.0 ± 2.1, r2 = 0.58). Accounting for the damage status of the adjacent cartilage improved the latter correlation (r2 = 0.77) and indicated that samples with adjacent damage such as fissures and avulsions had a diminished modulus–collagen/GAG relationship (p = 0.02). Quasi‐linear viscoelastic relaxation properties (C, τ1, and τ2) did not correlate with biochemical composition. We conclude that reduced matrix quantity decreases the equilibrium tensile modulus of human endplate cartilage and that characteristics of biochemical composition that are independent of matrix quantity, that is, characteristics related to matrix quality, may also be important. © 2013 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 32:245–252, 2014.
Evaluating the significance of expression of CEA mRNA and levels of CEA and its related proteins in colorectal cancer patients
Authors: Wang Wenyuan , Li Yaoping , Zhang Xin , Jing Jiexian , Zhao Xianwen , Wang Yan , Han Cunzhi
Published: November 2013

Objective

To explore the clinical significance of expression of CEA mRNA and serum CEA and the related proteins in colorectal cancer (CRC).

Methods

Blood samples were collected from 370 CRC patients and 350 controls. CEA mRNA was determined by RT‐PCR and levels of CEA, CA19‐9, CA242, and CA724 were examined with chemiluminescence.

Results

The positive rate of jointly detecting serum CEA, CA19‐9, CA242, and CA724 was significantly higher than CEA mRNA expressions (P < 0.01), both positive rates were significantly correlated with TNM stage, lymph node, and visceral metastasis. The positive rate of jointly detecting in patients with poorly differentiated tumor was significantly higher than that in patients with highly differentiated tumor (P < 0.01). By contrast, CEA mRNA expression was not related with histopathologic grading. Postoperative follow‐up found that all patients with high levels of CEA mRNA and serum CEA and the related proteins had liver, lung, pelvis, or other distant metastases.

Conclusions

These results suggest that high expressions of CEA mRNA and high levels of serum CEA and the related proteins are associated with the incidence and advanced of CRC. In addition, joint detection of serum CEA and the related proteins is more sensitivity than examination of serum CEA mRNA. J. Surg. Oncol. 2014 109:440–444. © 2013 Wiley Periodicals, Inc.
The Bidirectional Dyadic Association Between Tendency to Forgive, Self‐Esteem, Social Support, and PTSD Symptoms Among Terror‐Attack Survivors and Their Spouses
Authors: Weinberg Michael
Published: November 2013

This study examined the dyadic association of terror attack survivors’ and spouses’ internal resources, tendency to forgive (self, others, and situational forgiveness), self‐esteem, and the external resource of social support, as associated with victims’ and spouses’ posttraumatic stress disorder (PTSD) symptoms, using the actor–partner interdependence model. Based on lists by the One Family organization in Israel, 108 couples participated in the study. The study results demonstrate that in the dyad relationship, survivors’ tendency to forgive others and social support relate both to survivors’ decreased levels of PTSD symptom severity (β = −.20, p = .021; β = −.55 p < .001) and spouses’ decreased levels of PTSD symptom severity (β = −.21, p = .015; β = −.27, p = . 004), whereas spouses’ self‐esteem relates to both spouses’ and survivors’ decreased levels of PTSD symptom severity (β = −.57, p < .001; β = −.14, p = .041). The findings underscore the role of the survivor–spouse unit by highlighting the dyad relationship of internal and external resources as associated with both survivors’ and spouses’ PTSD symptoms. Theoretical and clinical implications of the findings are discussed.
Sociodemographic Risk, Developmental Competence, and PTSD Symptoms in Young Children Exposed to Interpersonal Trauma in Early Life
Authors: Enlow Michelle Bosquet , Blood Emily , Egeland Byron
Published: November 2013

Young children are disproportionately exposed to interpersonal trauma (maltreatment, witnessing intimate partner violence [IPV]) and appear particularly susceptible to negative sequelae. Little is known about the factors influencing vulnerability to traumatic stress responses and other negative outcomes in early life. This study examined associations among interpersonal trauma exposure, sociodemographic risk, developmental competence, and posttraumatic stress disorder (PTSD) symptoms in 200 children assessed from birth to first grade via standardized observations, record reviews, and maternal and teacher interviews. More severe PTSD symptoms were predicted by greater trauma exposure (r = .43), greater sociodemographic risk (r = .22), and lower developmental competence (rs = −.31 and −.54 for preschool and school‐age developmental competence, respectively). Developmental competence partially mediated the association between trauma exposure and symptoms. Trauma exposure fully mediated the association between sociodemographic risk and symptoms. Neither sociodemographic risk nor developmental competence moderated trauma exposure effects on symptoms. The findings suggest that (a) exposure to maltreatment and IPV has additive effects on posttraumatic stress risk in early life, (b) associations between sociodemographic adversity and poor mental health may be attributable to increased trauma exposure in disadvantaged populations, and (c) early exposures have a negative cascade effect on developmental competence and mental health.
Long‐term results and subjective outcome after gland‐preserving treatment in parotid duct stenosis
Authors: Koch Michael , Künzel Julian , Iro Heinrich , Psychogios Georgios , Zenk Johannes
Published: November 2013

Objectives/Hypothesis

To assess the objective long‐term results and subjective outcome after treatment of Stensen's duct stenosis.

Study Design

Retrospective study at a tertiary center.

Methods

The long‐term results after treatment with a minimally invasive regimen focusing on sialendoscopy were assessed in 82 patients with 98 parotid duct stenoses after primary gland‐preserving treatment. A questionnaire was used to assess the patients' perception of success, including clinical parameters and a visual analogue scale (VAS) assessing pain, symptoms, and salivary gland–related quality of life (QOL). Patients were invited to present for clinical and ultrasound examinations and sialendoscopy.

Results

The average follow‐up period was 98.48 months. Fifty percent of the patients reported having recurrent gland swelling; but only 19.5% reported recurrent pain and the VAS scores for current symptoms and pain were low. Independent of the type of stenosis, the VAS scores showed a significant reduction in symptoms and improvement in the perceived QOL after the treatment (P = 0.0001 each). Follow‐up examinations were carried out in 20.73% of the patients, and sialendoscopy was performed in 12.1% of the patients. After diagnosis, recurrent stenoses (n = 8, 9.75%) were successfully reopened in all cases. The glands were preserved in all of the patients.

Conclusion

Long‐term evaluation after minimally invasive treatment of stenoses of the parotid duct indicates that high success rates, high rates of gland preservation, and an acceptable subjective patient outcome can be achieved.

Level of Evidence

4. Laryngoscope, 124:1813–1818, 2014
Patient‐related and ENT‐related predictive factors based on the pain experienced during flexible nasendoscopy
Authors: Seccia Veronica , Dallan Iacopo , Massimetti Gabriele , Segnini Giovanni , Navari Elena , Fortunato Susanna , Bajraktari Arisa , Lenzi Riccardo , Muscatello Luca , Sellari‐Franceschini Stefano
Published: November 2013

Objectives/Hypothesis

The objective was to explore the role of specific patient‐related and operator‐related factors in pain perception during flexible laryngoscopy, which is one of the most common ENT procedures.

Study Design

Monocentric, randomized, individual prospective study.

Methods

A total of 532 patients (145 men and 387 women), without any relevant ENT diseases, underwent laryngoscopy performed by otolaryngologists with various degrees of experience. Patient discomfort was reported using visual analog scores, and willingness to repeat the experience was also recorded.

Results

Statistical analysis showed that greater pain was significantly associated with female patients and female otolaryngologists, whereas the pain was less severe in the cases of experienced laryngologists and older patients. Pain plays an important role in determining the willingness to repeat the examination; in fact, patients who experienced lower levels of pain during laryngoscopy were more prone to repeat the experience.

Conclusion

This article explores the importance of the extrinsic factors that are related to the patient and the otolaryngologist in determining the level of pain associated with laryngoscopy. Our study indicated that laryngoscopy is generally a well‐tolerated procedure, causing little overall discomfort, but that a subgroup of patients may experience more pain than others, which may affect the patient's perspective toward undergoing a similar future experience. Our analysis may be helpful for clinicians in understanding pain perception during a routine procedure, enabling them to focus more on that subgroup of patients who are more prone to pain.

Level of Evidence

1b. Laryngoscope, 124:1648–1652, 2014
Anti‐Infectious Surfaces Achieved by Polymer Modification
Authors: Gour Nidhi , Ngo Kien Xuan , Vebert‐Nardin Corinne
Published: November 2013

This review article presents the potential strategies of material surface modification by using polymeric approaches to design anti‐infectious materials. Supported by recent examples such as utilizing either microbe lethal or repelling properties, different strategies to the design of antimicrobial surfaces are reviewed. The deposition strategies for creating polymer modified antibacterial surfaces are described.
The average number of Sylow subgroups of a finite group
Authors: Moretó Alexander
Published: November 2013

We prove that if the average Sylow number (ignoring the Sylow numbers that are one) of a finite group G is ⩽7, then G is solvable.
CO2‐ and O2‐Sensitive Fluorophenyl End‐Capped Poly(ethylene glycol)
Authors: Choi Jung Yoon , Kim Jin Young , Moon Hyo Jung , Park Min Hee , Jeong Byeongmoon
Published: November 2013

Pentafluorophenyl end‐capped poly(ethylene glycol) (PF‐PEG‐PF) aqueous solution shows a lower critical solution temperature (LCST), which is sensitive to the type of gases dissolved in the solution. LCST increases from 24.5 to 26 °C when dissolved carbon dioxide is replaced by oxygen. The transparent‐to‐turbid transition is reversibly observed when the dissolved carbon dioxide in the PF‐PEG‐PF aqueous solution is exchanged with oxygen, and vice versa, at 24.5 °C. 19F NMR and 1H NMR spectra of the PF‐PEG‐PF in D2O suggest that 1) dehydration of PEG is the main reason of developing LCST of the PF‐PEG‐PF aqueous solution, 2) minute differences in the intermolecular interactions, as demonstrated by changes in the chemical shift of the PF‐PEG‐PF peaks, induce such a difference in LCST. This paper provides a new insight in designing a stimuli‐responsive polymer in that fine tuning of a phase transition can be controlled by the type of dissolved gas.

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Real‐time monitoring of exhaled drugs by mass spectrometry
Authors: Berchtold Christian , Bosilkovska Marija , Daali Youssef , Walder Bernhard , Zenobi Renato
Published: November 2013

Future individualized patient treatment will need tools to monitor the dose and effects of administrated drugs. Mass spectrometry may become the method of choice to monitor drugs in real time by analyzing exhaled breath. This review describes the monitoring of exhaled drugs in real time by mass spectrometry. The biological background as well as the relevant physical properties of exhaled drugs are delineated. The feasibility of detecting and monitoring exhaled drugs is discussed in several examples. The mass spectrometric tools that are currently available to analyze breath in real time are reviewed. The technical needs and state of the art for on‐site measurements by mass spectrometry are also discussed in detail. Off‐line methods, which give support and are an important source of information for real‐time measurements, are also discussed. Finally, some examples of drugs that have already been successfully detected in exhaled breath, including propofol, fentanyl, methadone, nicotine, and valproic acid are presented. Real‐time monitoring of exhaled drugs by mass spectrometry is a relatively new field, which is still in the early stages of development. New technologies promise substantial benefit for future patient monitoring and treatment. © 2013 Wiley Periodicals, Inc. Mass Spec Rev 33: 394–413, 2014
Closed‐Form Expressions for the Form Factor of a Polymer under Strong Confinement
Authors: Zorn Reiner
Published: November 2013

In this paper the scattering from an ideal polymer chain in strong confinement () is calculated. It is possible to derive analytical closed‐form expressions analogous to the Debye form factor. The results can be written in terms of one hypergeometric function 2F2 for all geometries (channel, film, unconfined). It is shown that the result is consistent with a recent calculation of the form factor for a polymer chain in a radial harmonic potential.
Crosstalk between VEGF and MTA1 signaling pathways contribute to aggressiveness of breast carcinoma
Authors: Nagaraj Sachin Raj M. , Shilpa Puttananjaiah , Rachaiah Kavitha , Salimath Bharathi P.
Published: November 2013

The expression of metastasis associated protein (MTA1) correlates well with tumor metastasis; however its role as a proangiogenic protein and the molecular mechanisms underlying the same are not fully understood. In this study the MTA1 protein was expressed and purified to evaluate its angiogenic potential. In both MCF‐7 and MDA‐MB‐231 cells, endogenous MTA1 protein was localized in the nucleus; while added recombinant MTA1 protein was bound to cell membrane as per immunofluorescence data. MTA1 was detected both in conditioned media and in human serum samples. Recombinant MTA1 regulated cellular functions of HUVEC's such as, proliferation, tube formation, and migration. MTA1 was more potent than VEGF in inducing invasion of breast cancer cells. Analogous to VEGF, MTA1 could induce angiogenesis in both non‐tumor and tumor context, as verified by rat cornea, shell less CAM and xenograft models respectively. However MTA‐1 was more potent an inducer of angiogenesis. VEGF or Flt‐1 gene promoter, luciferase gene reporter analysis revealed that MTA1 up regulates the expression of VEGF and its receptor Flt‐1 genes. Kinetics of VEGF‐induced expression of MTA1 and qPCR studies showed that there is an increased expression of MTA1 in tumor cells. VEGF induced phosphorylation of endogenous MTA1 on tyrosine residues; phosphorylation was mediated through VEGFR2 and p38‐MAP kinase. Recombinant MTA1 activated signaling, in MCF‐7 and MDA‐MB‐231 cells, involved ERK and JNK pathways. In conclusion, MTA1 is a potent angiogenic molecule and cross talk between VEGF and MTA1 protein regulates tumor angiogenesis and metastasis. © 2013 Wiley Periodicals, Inc.