bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical Composition and Antimicrobial Activity of the Essential Oil of Stachys officinalis (L.) Trevis. (Lamiaceae)
Authors: Lazarević Jelena S. , Ðorđević Aleksandra S. , Kitić Dušanka V. , Zlatković Bojan K. , Stojanović Gordana S.
Published: July 2013

Characterization by GC‐FID and GC/MS analyses of the Stachys officinalis (L.) Trevis. essential oil obtained by hydrodistillation of the aerial parts allowed the identification of 190 components that represented 97.9% of the total oil content. The main constituents identified were germacrene D (19.9%), β‐caryophyllene (14.1%), and α‐humulene (7.5%). Terpenoids were by far predominant (89.4%), with sesquiterpene hydrocarbons (69.1%) and oxygenated sesquiterpenes (14.8%) being the most abundant compounds detected in the oil. Based on the present and previously published results, multivariate statistical comparison of the chemical composition of the essential oils was performed within the species. Principal component analysis (PCA) and agglomerative hierarchical clustering (AHC) of the data on the volatile profiles of S. officinalis taxa revealed no pronounced differences among the samples originated from the Balkan Peninsula. Additionally, the oil was screened for in vitro antibacterial and antifungal activity using the broth microdilution assay. The oil's best antimicrobial activities were obtained against the mold Aspergillus niger (minimal inhibitory (MIC) and minimal fungicidal (MFC) concentrations of 2.5 and 5.0 mg/ml, resp.) and the yeast Candida albicans (MIC and MFC of 5.0 mg/ml).
Cyclopaldic Acid, Seiridin, and Sphaeropsidin A as Fungal Phytotoxins, and Larvicidal and Biting Deterrents against Aedes aegypti (Diptera: Culicidae): StructureActivity Relationships
Authors: Cimmino Alessio , Andolfi Anna , Avolio Fabiana , Ali Abbas , Tabanca Nurhayat , Khan Ikhlas A. , Evidente Antonio
Published: July 2013

Aedes aegypti L. is the major vector of the arboviruses responsible for dengue fever, one of the most devastating human diseases. From a preliminary screening of fungal phytotoxins, cyclopaldic acid (1), seiridin (2), sphaeropsidin A (4), and papyracillic acid (5) were evaluated for their biting deterrent and larvicidal activities against Ae. aegypti L. Because compounds 1, 2, 4, and 5 exhibited mosquito biting deterrent activities and 1 and 4 demonstrated larvicidal activities, further structureactivity relationship studies were initiated on these toxins. In biting‐deterrence bioassays, 1, 2, 4, and 5, 3,8‐didansylhydrazone of cyclopaldic acid, 1F, 5‐azidopentanoate of cyclopaldic acid A, 1G, the reduced derivative of cyclopaldic acid, 1 H, isoseiridin (3), 2′‐O‐acetylseiridin (2A), 2′‐oxoseiridin (2C), 6‐O‐acetylsphaeropsidin A (4A), 8,14‐methylensphaeropsidin A methyl ester (4B), and sphaeropsidin B (4C) showed activities higher than the solvent control. Sphaeropsidin B (4C) was the most active compound followed by 2A, while the other compounds were less active. Biting‐deterrence activity of compound 4C was statistically similar to DEET. In the larvicidal screening bioassays, only compounds 1 and 4 demonstrated larvicidal activities. Based on LD50 values, compound 4 (LD50 36.8 ppm) was significantly more active than compound 1 (LD50 58.2 ppm). However, the activity of these compounds was significantly lower than permethrin.
Biogeographical Patterns and Phenological Changes in Lapiedra martineziiLag. Related to Its Alkaloid Diversity
Authors: Ríos Segundo , Berkov Strahil , Martínez‐Francés Vanessa , Bastida Jaume
Published: July 2013

The aim of this work was to investigate the alkaloid patterns of Lapiedra martinezii and their relation to biogeography and phenology focused in a phylogenetic comparison. Plants from 14 populations of L. martinezii, covering almost its entire distribution area, were subjected to morphological, ecological, and phytochemical analysis. Experiments for different alkaloid‐type content are proposed as a new tool for analysis of plant distribution. Several plants were transplanted for weekly observation of their phenological changes, and alkaloids from different plant organs were extracted, listed, and compared. The alkaloid pattern of L. martinezii comprises 49 compounds of homolycorine, lycorine, tazettine, haemantamine, and narciclasine types. The populations located in the north and south margins of the distribution area displayed alkaloid patterns different from those of the central area. Changes in these patterns during their phenological cycle may be related to a better defence for plant reproduction. L. martinezii is an old relict plant, and it has maintained some of the more primitive morphological features and alkaloid profiles of the Mediterranean Amaryllidaceae. The variations in alkaloid content observed could be interpreted in a phylogenetic sense, and those found in their phenological changes, in an adaptive one.
Structural Characterization and Chemical Classification of Some Bryophytes Found in Latvia
Authors: Maksimova Viktorija , Klavina Laura , Bikovens Oskars , Zicmanis Andris , Purmalis Oskars
Published: July 2013

Bryophytes are the second largest taxonomic group in the plant kingdom; yet, studies conducted to better understand their chemical composition are rare. The aim of this study was to characterize the chemical composition of bryophytes common in Northern Europe by using elemental, spectral, and non‐destructive analytical methods, such as Fourier transform IR spectrometry (FT‐IR), solid‐phase 13C‐NMR spectrometry, and pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), for the purpose of investigating their chemotaxonomic relationships on the basis of chemical‐composition data. The results of all these analyses showed that bryophytes consist mainly of carbohydrates. Judging by FT‐IR spectra, the OH groups in combination of CO groups were the most abundant groups. The 13C‐NMR spectra provided information on the presence of such compounds as phenolics and lipids. It was found that the amount of phenolic compounds in bryophytes is relatively small. This finding definitely confirmed the absence of lignin in the studied bryophytes. Cluster analysis was used to better understand differences in the chemical composition of bryophyte samples and to evaluate possible usage of these methods in the chemotaxonomy of bryophytes.
Naphtho‐γ‐pyrones from Endophyte Aspergillus niger Occurring in the Liverwort Heteroscyphus tener (Steph.) Schiffn.
Authors: Li Xiao‐Bin , Xie Fei , Liu Shan‐Shan , Li Ying , Zhou Jin‐Chuan , Liu Yong‐Qing , Yuan Hui‐Qing , Lou Hong‐Xiang
Published: July 2013

Bioactivity‐guided fractionation of the cytotoxic extract of Aspergillus niger, an endophytic fungus from the Chinese liverwort Heteroscyphus tener (Steph.) Schiffn., afforded five new naphtho‐γ‐pyrones, rubrofusarin‐6‐O‐α‐D‐ribofuranoside (1), (R)‐10‐(3‐succinimidyl)‐TMC‐256A1 (2), asperpyrone E (3), isoaurasperone A (4), and isoaurasperone F (5), as well as four known ones, dianhydroaurasperone C (6), aurasperone D (7), asperpyrone D (8), and asperpyrone A (9), together with a cytotoxic cyclic pentapeptide, malformin A1 (10). Their structures were determined by extensive spectroscopic analysis. The absolute configurations of dimeric naphtho‐γ‐pyrones 3–9 were also determined by analysis of their respective CD spectra.
Enantiomeric and Diastereoisomeric (Mixed) L/ D‐Octaarginine Derivatives – A Simple Way of Modulating the Properties of Cell‐Penetrating Peptides
Authors: Purkayastha Nirupam , Eyer Klaus , Robinson Tom , Dittrich Petra S. , Beck Albert K. , Seebach Dieter , Kolesinska Beata , Cadalbert Riccardo
Published: July 2013

Cell‐penetrating peptides (CPPs) are promising vehicles for delivery of drugs, antibiotics, proteins, nucleic acid derivatives, etc. into eukaryotic and prokaryotic target cells. To prevent premature degradation, CPPs consisting of D‐ or β‐amino acid residues have been used. We present simple models for the various modes of delivery of physiologically active cargoes by CPPs, depending on the nature of their conjugation (Fig. 1), and we describe the plasma stability of oligoarginines (OAs) 1–4, the most common unnatural CPPs. Fluorescein‐labeled L‐octaarginine 1 was found to have a half‐life (t1/2) of <0.5 min, the D‐enantiomer (2) of >7 d (Fig. 2). For possible medicinal applications, the former type of derivative would be too unstable, and the latter one undesirably persistent. Thus, seven of the 256 possible ‘mixed’ Flua‐L/D‐octaarginine amides, 4a–4g, were synthesized and shown to have half‐lives in heparine‐stabilized human plasma between 8 min and 5.5 h (Figs. 3 and 4). The cell penetration of the new OAs was investigated with ‘healthy’ and with apoptotic HEK cells (Figs. 5–8), and their interactions with phospholipid bilayers were studied, using anionic lipid vesicles (Figs. 9 and 10). There are surprisingly large differences in the rates of cell penetration and binding to vesicle walls between the various stereoisomeric octaarginine derivatives 1, 2, and 4a–4g (Figs. 5 and 7). – The role of D‐amino acids and D‐peptides in nature and in drug design is briefly discussed and referenced.
Light‐Induced Bistability in the 2 D Coordination Network {[Fe(bbtr)3][BF4]2}∞: Wavelength‐Selective Addressing of Molecular Spin States
Authors: Chakraborty Pradip , Pillet Sebastien , Bendeif El‐Eulmi , Enachescu Cristian , Bronisz Robert , Hauser Andreas
Published: July 2013

Whereas the neat polymeric FeII compound {[Fe(bbtr)3][ClO4]2}∞ (bbtr=1,4‐di(1,2,3‐triazol‐1‐yl)butane) shows an abrupt spin transition centered at 107 K facilitated by a crystallographic symmetry breaking, in the covalently linked 2D coordination network of {[Fe(bbtr)3][BF4]2}∞, FeII stays in the high‐spin state down to 10 K. However, strong cooperative effects of elastic origin result in reversible, persistent, and wavelength‐selective photoswitching between the low‐spin and high‐spin manifolds. This compound thus shows true light‐induced bistability below 100 K. The persistent bidirectional optical switching behavior is discussed as a function of temperature, irradiation time, and intensity. Crystallographic studies reveal a photoinduced symmetry breaking and serve to establish the correlation between structure and cooperative effects. The static and kinetic behavior is explicated within the framework of the mean‐field approximation.
Modular Columnar Supramolecular Polymers as Scaffolds for Biomedical Applications
Authors: Petkau‐Milroy Katja , Sonntag Michael H. , Brunsveld Luc
Published: July 2013

Self‐assembly of discotic molecules into supramolecular polymers offers a flexible approach for the generation of multicomponent one‐dimensional columnar architectures with tuneable biomedical properties. Decoration with ligands induces specific binding of the self‐assembled scaffold to biological targets. The modular design allows the easy co‐assembly of different discotics for the generation of probes for targeted imaging and cellular targeting with adjustable ligand density and composition.
A Conformationally Flexible Dinuclear PtII Complex with Differential Behavior of its Two States toward Quadruplex DNA
Authors: von Grebe Philipp , Suntharalingam Kogularamanan , Vilar Ramon , Sanz Miguel Pablo J. , Herres‐Pawlis Sonja , Lippert Bernhard
Published: July 2013

The reaction of tetrakis(pyridine‐2‐yl)pyrazine (tppz) with 2 equiv of (2,2′‐bpy)PtII in water yields two isomeric dinuclear cations, [{Pt(2,2′‐bpy)}2(tppz)]4+, in which Pt coordination exclusively takes place through the two pairs of pyridine‐2‐yl nitrogen atoms. The two conformational isomers differ in their overall shape, with the formation of “Z” and “U” shapes, which are formed at 40 °C (Z isomer, 1) and under reflux conditions (U isomer, 2), respectively. X‐ray crystal‐structure analyses of the Z isomer, [{Pt(2,2′‐bpy)}2(tppz)](PF6)4⋅3 CHCl3⋅4 H2O (1 a), and of the U isomer, [{Pt(2,2′‐bpy)}2](PF6)4⋅2 CH3CN⋅1.5 H2O (2 a), were carried out. Co‐crystallization of compound 2 with PtCl2(2,2′‐bpy) yielded [{Pt(2,2′‐bpy)}2(tppz)](BF4)4⋅[PtCl2(2,2′‐bpy)]⋅4.5 H2O (3), in which the PtCl2(2,2′‐bpy) entity was sandwiched between the two 2,2′‐bpy faces of the U‐shaped cation (2). Quantum chemical calculations revealed that the U isomer was more stable than the Z isomer, both in the gas phase and in an aqueous environment. These two isomers display different affinities toward duplex DNA and human telomeric quadruplex DNA (Htelo), as concluded from CD spectroscopy and FID assays. Thus, the U isomer binds significantly more strongly to quadruplex DNA (DC50=0.38 μM) than the Z isomer (DC50=8.50 μM).
Cu‐Catalyzed Formal Methylative and Hydrogenative Carboxylation of Alkynes with Carbon Dioxide: Efficient Synthesis of α,β‐Unsaturated Carboxylic Acids
Authors: Takimoto Masanori , Hou Zhaomin
Published: July 2013

The sequential hydroalumination or methylalumination of various alkynes catalyzed by different catalyst systems, such those based on Sc, Zr, and Ni complexes, and the subsequent carboxylation of the resulting alkenylaluminum species with CO2catalyzed by an N‐heterocyclic carbene (NHC)–copper catalyst have been examined in detail. The regio‐ and stereoselectivity of the overall reaction relied largely on the hydroalumination or methylalumination reactions, which significantly depended on the catalyst and alkyne substrates. The subsequent Cu‐catalyzed carboxylation proceeded with retention of the stereoconfiguration of the alkenylaluminum species. All the reactions could be carried out in one‐pot to afford efficiently a variety of α,β‐unsaturated carboxylic acids with well‐controlled configurations, which are difficult to construct by previously reported methods. This protocol could be practically useful and attractive because of its high regio‐ and stereoselectivity, simple one‐pot reaction operation, and the use of CO2as a starting material.
Self‐Assembly versus Stepwise Synthesis: Heterometal–Organic Frameworks Based on Metalloligands with Tunable Luminescence Properties
Authors: Zhang Shu‐Ran , Du Dong‐Ying , Tan Ke , Qin Jun‐Sheng , Dong Hui‐Qing , Li Shun‐Li , He Wen‐Wen , Lan Ya‐Qian , Shen Ping , Su Zhong‐Min
Published: July 2013

A new family of heterometal–organic frameworks has been prepared by two synthesis strategies, in which IFMC‐26 and IFMC‐27 are constructed by self‐assembly and IFMC‐28 is obtained by stepwise synthesis based on the metalloligand (IFMC=Institute of Functional Material Chemistry). IFMC‐26 is a (3,6)‐connected net and IFMC‐27 is a (4,8)‐connected 3D framework. The metalloligands {Ni(H4L)}(NO3)2 are connected by binuclear lanthanide clusters giving rise to a 2D sheet structure in IFMC‐28. Notably, IFMC‐26‐EuxTby and IFMC‐28‐EuxTby have been obtained by changing the molar ratios of raw materials. Owing to the porosity of IFMC‐26, Tb3+@IFMC‐26‐Eu and Eu3+@IFMC‐26‐Tb are obtained by postencapsulating TbIII and EuIII ions into the pores, respectively. Tunable luminescence in metal–organic frameworks is achieved by the two kinds of doping methods. In particular, the quantum yields of heterometal–organic frameworks are apparently enhanced by postencapsulation of LnIII ions.
Formation and Geometrical Control of Polygon‐Like Metal‐Coordination Assemblies
Authors: Maeda Hiromitsu , Akuta Ryo , Bando Yuya , Takaishi Kazuto , Uchiyama Masanobu , Muranaka Atsuya , Tohnai Norimitsu , Seki Shu
Published: July 2013

Polygon‐like [2+2]‐ and [3+3]‐type metal complexes were prepared from dipyrrin dimers connected by acute‐angled spacers. The electrical conduction depends strongly on the packing alignment of the compounds, revealing the presence of effective hopping pathways for holes with relatively high mobility up to 0.11 cm2 V−1 s−1 along the aligned axis of [3+3]‐type metal‐bridged assemblies. These observations correlated with the geometrical control of the π‐conjugated metal complexes in the cyclic structures, which enables their ordered arrangement in the assemblies.
Preparative Separation of Enantiomers Based on Functional Nucleic Acids Modified Gold Nanoparticles
Authors: Huang Rong , Wang Daifang , Liu Shuzhen , Guo Longhua , Wang Fangfang , Lin Zhenyu , Qiu Bin , Chen Guonan
Published: July 2013

The preparative‐scale separation of chiral compounds is vitally important for the pharmaceutical industry and related fields. Herein we report a simple approach for rapid preparative separation of enantiomers using functional nucleic acids modified gold nanoparticles (AuNPs). The separation of DL‐tryptophan (DL‐Trp) is demonstrated as an example to show the feasibility of the approach. AuNPs modified with enantioselective aptamers were added into a racemic mixture of DL‐Trp. The aptamer‐specific enantiomer (L‐Trp) binds to the AuNPs surface through aptamer‐L‐Trp interaction. The separation of DL‐Trp is then simply accomplished by centrifugation: the precipitate containing L‐Trp bounded AuNPs is separated from the solution, while the D‐Trp remains in the supernatant. The precipitate is then redispersed in water. The aptamer is denatured under 95 °C and a second centrifugation is then performed, resulting in the separation of AuNPs and L‐Trp. The supernatant is finally collected to obtain pure L‐Trp in water. The results show that the racemic mixture of DL‐Trp is completely separated into D‐Trp and L‐Trp, respectively, after 5 rounds of repeated addition of fresh aptamer‐modified AuNPs to the DL‐Trp mixture solution. Additionally, the aptamer‐modified AuNPs can be repeatedly used for at least eight times without significant loss of its binding ability because the aptamer can be easily denatured and renatured in relatively mild conditions. The proposed approach could be scaled up and extended to the separation of other enantiomers by the adoption of other enantioselective aptamers. Chirality 25:751–756, 2013. © 2013 Wiley Periodicals, Inc.
Self‐Assembly Structures of 1H‐Indazoles in the Solution and Solid Phases: A Vibrational (IR, FIR, Raman, and VCD) Spectroscopy and Computational Study
Authors: Avilés Moreno J. R. , Quesada Moreno M. M. , López González J. J. , Claramunt R. M. , López C. , Alkorta I. , Elguero J.
Published: July 2013

1H‐indazoles are good candidates for studying the phenomena of molecular association and spontaneous resolution of chiral compounds. Thus, because the 1H‐indazoles can crystallize as dimers, trimers, or catemers, depending on their structure and the phase that they are in, the difficulty in the experimental analysis of the structure of the family of 1H‐indazoles becomes clear. This difficulty leads us to contemplate several questions: How can we determine the presence of different structures of a given molecular species if they change according to the phase? Could these different structures be present in the same phase simultaneously? How can they be determined? To shed light on these questions, we outline a very complete strategy by using various vibrational spectroscopic techniques that are sensitive (VCD) and insensitive (IR, FIR, and Raman) towards the chirality, together with quantum chemical calculations.
Commentary on ‘Interventions for promoting re‐integration and reducing harmful behaviour and lifestyles in street‐connected children and young people’ with a response from the review authors
Authors: Christian Rahila U. , Coren Esther , Hossain Rosa
Published: July 2013

This is a commentary on a Cochrane review, published in the issue of EBCH, first published as: Coren E, Hossain R, Pardo Pardo J, Veras MMS, Chakraborty K, Harris H, Martin AJ. Interventions for promoting re‐integration and reducing harmful behaviour and lifestyles in street‐connected children and young people. Cochrane Database of Systematic Reviews 2013, Issue 2. Art. No.: CD009823. DOI: 10.1002/14651858.CD009823.pub2.
Commentaries on ‘Procalcitonin to initiate or discontinue antibiotics in acute respiratory tract infections’ with a response from the review authors
Authors: Sabhaney Vikram , Enarson Paul , Irwin Adam D. , Carrol Enitan D. , Schuetz Philipp , Briel Matthias , Bucher Heiner C. , Mueller Beat ,   for the Procalcitonin‐stewardship study group
Published: July 2013

These are commentaries on a Cochrane review, published in this issue of EBCH, first published as: Schuetz P, Müller B, Christ‐Crain M, Stolz D, Tamm M, Bouadma L, Luyt CE, Wolff M, Chastre J, Tubach F, Kristoffersen KB, Burkhardt O, Welte T, Schroeder S, Nobre V, Wei L, Bhatnagar N, Bucher HC, Briel M. Procalcitonin to initiate or discontinue antibiotics in acute respiratory tract infections. Cochrane Database of Systematic Reviews 2012, Issue 9. Art. No.: CD007498. DOI: 10.1002/14651858.CD007498.pub2.
In Situ X‐ray Absorption Spectroscopy and Nonclassical Catalytic Hydrogenation with an Iron(II) Catecholate Immobilized on a Porous Organic Polymer
Authors: Kraft Steven J. , Hu Bo , Zhang Guanghui , Miller Jeffrey T. , Hock Adam S.
Published: July 2013

The oxidation state and coordination number of immobilized iron catecholate EtO2Fe(CAT‐POP) were determined by X‐ray absorption spectroscopy (XAS) under a variety of conditions. We find the as‐prepared material to be three‐coordinate Fe2+ that readily oxidizes to Fe3+ upon exposure to air but remains three‐coordinate. Both the reduced and oxidized Fe(CAT‐POP) catalyze olefin hydrogenation in batch and flow reactors. We determined the catalytic rates for both species and also observed by means of XAS that the oxidation state of the iron centers does not change in hydrogen at the reaction temperature. Therefore, we postulate that the mechanism of hydrogenation by Fe(CAT‐POP) proceeds through one of several possible nonclassical mechanisms, which are discussed.
Analysis of the Hysteretic Behaviour of 3D Spin Crossover Compounds by Using an Ising‐Like Model
Authors: Chiruta Daniel , Linares Jorge , Garcia Yann , Dahoo Pierre Richard , Dimian Mihai
Published: July 2013

Invited for the cover of this issue is the European spin‐crossover team led by Prof. Linares and Prof. Garcia. They share with us their passion for spin‐crossover science. The cover image shows a thermally induced two‐step spin conversion with hysteresis as reflected by the modelling of 3D spin‐crossover compound [Fe(btr)3](ClO4)2, whose crystal structure is shown in the background.
Rhodium‐Catalyzed Cyclization Reactions of γ‐Alkynyl Aldehydes with Carboxylic Acid Anhydrides
Authors: Tajima Yuki , Kobayashi Masayuki , Noguchi Keiichi , Tanaka Ken
Published: July 2013

It has been established that a cationic rhodium(I)/H8‐binap or binap complex catalyzes two different modes of cyclization of γ‐alkynyl aldehydes with carboxylic acid anhydrides to give cyclic aldehyde gem‐dicarboxylates and cyclic alkenyl esters through cleavage of the carboxylic acid anhydride C–O bond. The reaction of a terminal γ‐alkynyl aldehyde with diethyl pyrocarbonate afforded a cyclic allylic carbonate with a high ee value.
Efficiency of the Free‐Radical Hydrophosphonylation of Alkenes: The Photoinduced Reaction of Dimethyl H‐Phosphonate with Enopyranoses as an Exemplary Case
Authors: Dondoni Alessandro , Staderini Samuele , Marra Alberto
Published: July 2013

Free‐radical hydrophosphonylation of alkenes by H‐phosphonates has been reported by other groups to occur under harsh conditions. On the other hand, we demonstrate in this paper that the hydrophosphonylation of alkene functionalized carbohydrates (enopyranoses) by dimethyl H‐phosphonate can be carried out with high efficiency under neutral conditions at room temperature and with short reaction times using UV/Vis light irradiation in the presence of a suitable photoinitiator. Indeed, a range of structurally different allyl C‐glycosides and exo‐glycals were transformed into the corresponding glycosylalkyl phosphonates that were isolated in excellent yields (88–98 %), except for one case (45 %). A mechanism similar to that of the free‐radical photoinduced hydrothiolation of alkenes is proposed.
When are two pieces better than one: fitting and testing OLS and RMA regressions
Authors: Friedman Jane , Bohonak Andrew J. , Levine Richard A.
Published: July 2013

This paper describes a new method of choosing between a simple linear and a two‐phase linear reduced major axis regression model. For continuous two‐phase linear models, differential evolution is used to estimate the parameters. The method can be used with either ordinary least squares or reduced major axis regression. There are no other methods in the literature for fitting two‐phase reduced major axis regressions. Our new method is applied to problems in zebrafish kinetics bedload transport and a classic linear model of cricket chirping. Copyright © 2013 John Wiley & Sons, Ltd.
How accurate are physical property estimation programs for organosilicon compounds?
Authors: Boethling Robert , Meylan William
Published: July 2013

Organosilicon compounds are important in chemistry and commerce, and nearly 10% of new chemical substances for which premanufacture notifications are processed by the US Environmental Protection Agency (USEPA) contain silicon (Si). Yet, remarkably few measured values are submitted for key physical properties, and the accuracy of estimation programs such as the Estimation Programs Interface (EPI) Suite and the SPARC Performs Automated Reasoning in Chemistry (SPARC) system is largely unknown. To address this issue, the authors developed an extensive database of measured property values for organic compounds containing Si and evaluated the performance of no-cost estimation programs for several properties of importance in environmental assessment. These included melting point (mp), boiling point (bp), vapor pressure (vp), water solubility, n-octanol/water partition coefficient (log KOW), and Henry's law constant. For bp and the larger of 2 vp datasets, SPARC, MPBPWIN, and the USEPA's Toxicity Estimation Software Tool (TEST) had similar accuracy. For log KOW and water solubility, the authors tested 11 and 6 no-cost estimators, respectively. The best performers were Molinspiration and WSKOWWIN, respectively. The TEST's consensus mp method outperformed that of MPBPWIN by a considerable margin. Generally, the best programs estimated the listed properties of diverse organosilicon compounds with accuracy sufficient for chemical screening. The results also highlight areas where improvement is most needed. Environ Toxicol Chem 2013;32:2433–2440. © 2013 SETAC
Analyzing comprehensive palatability of cheese products by multivariate regression to its subdomains
Authors: Nakano Kumiko , Kyutoku Yasushi , Sawa Minako , Matsumura Shigenobu , Dan Ippeita , Fushiki Tohru
Published: July 2013

The present study explored the possibility of generating a novel sensory evaluation instrument for describing comprehensive food palatability via its subdomains (rewarding, cultural, and informational) while keeping physiological factors constant. Seventy‐five Japanese participants were asked to taste cheese samples and to respond to a questionnaire that was developed to dissect the distinct subdomains of palatability. The subsequent factor analyses revealed that three major factors may serve as distinct subdomains of palatability: rewarding, cultural, and informational, although the informational factor was not sufficiently robust. Multivariate regression analysis on cheese samples with exactly the same ingredients but sold in different packages led to different comprehensive palatability ratings due to the contribution of the cultural, but not the rewarding, factor. These results suggest that palatability is not merely determined by the physical and chemical properties that are intrinsic to a food product itself, but also depends on psychological properties that can arise through interaction between humans and the food product. The current study presents the first experimental demonstration that palatability could be dissociated to its subdomains.
Effect of gamma irradiation on physicochemical properties of stored pigeon pea (Cajanus cajan) flour
Authors: Bamidele Oluwaseun P. , Akanbi Charles T.
Published: July 2013

The effect of gamma irradiation at various doses (5, 10, 15, 20 kGy) was observed on pigeon pea flour stored for 3 months on proximate composition, functional properties, and peroxide value. Sensory evaluation was also carried out on bean cake (moinmoin) made from nonirradiated and irradiated pigeon pea flour. The results showed that stored gamma‐irradiated samples had significantly lower (P < 0.05) value of protein and little or no effect on moisture content. There were slight decreases in crude fiber and ash content of the irradiated samples compared with the control sample. The result of functional properties of the irradiated flours showed slight increase in water absorption capacity, swelling capacity and bulk density. The peroxide value of crude oil increased significantly with dose increases for the period of storage. The sensory evaluation of moinmoin samples prepared from irradiated pigeon pea flour showed no significant difference from the moinmoin sample prepared from nonirradiated flour. It can be concluded that gamma irradiation can extend the shelf life of pigeon pea flour.
The importance of crop growth modeling to interpret the Δ14CO2 signature of annual plants
Authors: Bozhinova D. , Combe M. , Palstra S. W. L. , Meijer H. A. J. , Krol M. C. , Peters W.
Published: July 2013

The 14C/C abundance in CO2(Δ14CO2) promises to provide useful constraints on regional fossil fuel emissions and atmospheric transport through the large gradients introduced by anthropogenic activity. The currently sparse atmospheric Δ14CO2 monitoring network can potentially be augmented by using plant biomass as an integrated sample of the atmospheric Δ14CO2. But the interpretation of such an integrated sample requires knowledge about the day‒to‒day CO2 uptake of the sampled plants. We investigate here the required detail in daily plant growth variations needed to accurately interpret regional fossil fuel emissions from annual plant samples. We use a crop growth model driven by daily meteorology to reproduce daily fixation of Δ14CO2 in maize and wheat plants in the Netherlands in 2008. When comparing the integrated Δ14CO2 simulated with this detailed model to the values obtained when using simpler proxies for daily plant growth (such as radiation and temperature), we find differences that can exceed the reported measurement precision of Δ14CO2(∼2‰). Furthermore, we show that even in the absence of any spatial differences in fossil fuel emissions, differences in regional weather can induce plant growth variations that result in spatial gradients of up to 3.5‰ in plant samples. These gradients are even larger when interpreting separate plant organs (leaves, stems, roots, or fruits), as they each develop during different time periods. Not accounting for these growth‒induced differences in Δ14CO2 in plant samples would introduce a substantial bias (1.5–2 ppm) when estimating the fraction of atmospheric CO2 variations resulting from nearby fossil fuel emissions.
Two distinct roles of Atlantic SSTs in ENSO variability: North Tropical Atlantic SST and Atlantic Niño
Authors: Ham Yoo‐Geun , Kug Jong‐Seong , Park Jong‐Yeon
Published: July 2013

Two distinct roles of the Atlantic sea surface temperatures (SSTs), namely, the North Tropical Atlantic (NTA) SST and the Atlantic Niño, on the El Niño–Southern Oscillation (ENSO) variability are investigated using the observational data from 1980 to 2010 and coupled model experiments. It appears that the NTA SST and the Atlantic Niño can be used as two independent predictors for predicting the development of ENSO events in the following season. Furthermore, they are likely to be linked to different types of El Niño events. Specifically, the NTA SST cooling during February, March, and April contributes to the central Pacific warming at the subsequent winter season, while the negative Atlantic Niño event during June, July, and August contributes to enhancing the eastern Pacific warming. The coupled model experiments support these results. With the aid of a lagged inverse relationship, the statistical forecast using two Atlantic indices can successfully predict various ENSO indices.
Universal structure of mesoscale eddies in the ocean
Authors: Zhang Zhengguang , Zhang Yu , Wang Wei , Huang Rui Xin
Published: July 2013

Mesoscale eddies dominate oceanic kinetic energy at sub‐initial frequencies. Their three‐dimensional structure has, however, remained obscure, hindering better understanding of eddy dynamics. Here by applying the composite analysis of satellite altimetry and Argo float data to the globe, we show that despite remarkable regional differences in amplitude, extent and polarity, etc., mesoscale eddies have a universal structure in normalized stretched coordinates. Horizontally, the associated pressure anomaly is well described by a function of the normalized radial distance from the eddy center R(rn)=(1−rn2/2)· exp(−rn2/2), whereas vertically it is sinusoidal in a stretched coordinate , where N and f are the buoyancy frequency and the Coriolis parameter.
Ultrasound‐guided intranodal lymphangiography followed by thoracic duct embolization for treatment of postoperative bilateral chylothorax
Authors: Parvinian Ahmad , Mohan Girish C. , Gaba Ron C. , Saldanha David F. , Knuttinen M. Grace , Bui James T. , Minocha Jeet
Published: July 2013

Background

Percutaneous thoracic duct embolization (TDE) is a safe, effective, and minimally invasive option for treating chylothorax. A recent report demonstrated the feasibility of ultrasound‐guided intranodal lymphangiography as an alternative to pedal lymphangiography for visualization of the thoracic duct, promising relative technical ease and decreased procedure time for TDE.

Methods

We report a case of postoperative bilateral chylothorax treated with ultrasound‐guided intranodal lymphangiography followed by TDE.

Results

Intranodal lymphangiography resulted in rapid opacification of the abdominal lymphatics, permitting technically successful primary and secondary embolization procedures. Deployment of metallic coils and liquid embolic agents within the thoracic duct produced rapid clinical and radiographic improvement.

Conclusion

Intranodal lymphangiography is a reliable, reproducible, and less technically challenging alternative to pedal lymphangiography. © 2013 Wiley Periodicals, Inc. Head Neck 36: E21–E24, 2014
Toxicities and costs of placing prophylactic and reactive percutaneous gastrostomy tubes in patients with locally advanced head and neck cancers treated with chemoradiotherapy
Authors: Baschnagel Andrew M. , Yadav Siddhartha , Marina Ovidiu , Parzuchowski Aaron , Lanni Thomas B. , Warner Jillian N. , Parzuchowski Jeanne S. , Ignatius Renjitha T. , Akervall Jan , Chen Peter Y. , Krauss Daniel J.
Published: July 2013

Background

We compared dependence rates, complications, toxicities, and costs associated with prophylactic versus reactive percutaneous endoscopic gastrostomy (PEG) tube placement.

Methods

One hundred ninety‐three patients with locally advanced head and neck squamous cell carcinoma treated with concurrent chemoradiotherapy were retrospectively reviewed.

Results

The 1‐year and 2‐year actuarial PEG tube dependence rate of the entire cohort was 24% and 13%, respectively. There was no difference in the PEG tube dependence rates between those placed prophylactically versus reactively. Patients who received a PEG tube reactively had a significantly higher stricture rate (p = .03) and aspiration rate (p < .001) compared to the prophylactic group. There were significantly fewer hospitalizations in the prophylactic group compared to the reactive group (p = .003). When accounting for both PEG placement and hospitalizations, the prophylactic approach was found to be more cost effective.

Conclusion

PEG tubes placed prophylactically were associated with lower rates of strictures, aspirations, hospitalizations, and costs compared to those placed reactively. © 2013 Wiley Periodicals, Inc. Head Neck 36: 1155–1161, 2014
An Expeditious Synthesis of Flavonols Promoted by Montmorillonite KSF Clay and Assisted by Microwave Irradiation under Solvent‐Free Conditions
Authors: Babu Mariappan , Pitchumani Kasi , Ramesh Penugonda
Published: July 2013

A simple, efficient, rapid, and ecofriendly synthesis of flavonols in >90% yield from 2′‐(mesyloxy)epoxychalcones (=2‐(3‐aryl‐2,3‐epoxypropanoyl)phenyl methanesulfonates) promoted by montmorillonite KSF clay and assisted by microwave irradiation has been described.
Petrorhagiosides A – D, New γ‐Pyrone Derivatives from Petrorhagia saxifragaLink
Authors: D'Abrosca Brigida , Pacifico Severina , Scognamiglio Monica , Tsafantakis Nikolaos , Pagliari Emanuela , Monaco Pietro , Fiorentino Antonio
Published: July 2013

Four novel γ‐pyrone (=4H‐pyran‐4‐one) metabolites, petrorhagiosides A–D, along with four known analogs, have been isolated from the MeOH extract of Petrorhagia saxifraga, a perennial herbaceous plant typical of Mediterranean vegetation. The structures of the new compounds were established on the basis of extensive spectroscopic analyses including 1D‐ an 2D‐NMR (1H,1H‐DQ‐COSY, TOCSY, HSQC, CIGAR‐HMBC, and HSQC‐TOCSY) experiments.
Nucleophilic Reactivity of Ethers Against Terminal Epoxides in the Presence of BF3: A Mechanistic Study
Authors: Kose Aytekin , Altundas Ramazan , Seçen Hasan , Kara Yunus
Published: July 2013

In the presence of BF3, a series of symmetrical and unsymmetrical ethers reacted with epichlorohydrin and 2‐[(benzyloxy)methyl]oxirane, two terminal epoxides, to afford 1‐alkoxy‐3‐chloropropan‐2‐ol and 1‐alkoxy‐3‐(benzyloxy)propan‐2‐ol. The cleavage of unsymmetrical ethers occurred via an SN2 or SN1 mechanism. Secondary epoxides did not give similar ring‐opening products.
Organic Stereochemistry. Part 7
Authors: Testa Bernard
Published: July 2013

This review continues a general presentation of the principles of stereochemistry with special emphasis on the biomedicinal sciences. Here, we discuss and illustrate the phenomenon of substrate stereoselectivity in biochemistry (endogenous metabolism) and principally in xenobiochemistry or drug metabolism. The review begins with an overview of the stereoselective processes occurring in the biomedicinal sciences. The general rule is for distinct stereoisomers, be they enantiomers or diastereoisomers, to elicit different pharmacological responses (Part 5), to a lesser extent be transported with different efficacies (Part 5), and to be metabolized at different rates (this Part). In other words, biological environments discriminate between stereoisomers both when acting on them and when being acted upon by them. The concept of substrate stereoselectivity describes this phenomenon in endogenous biochemistry and xenobiotic metabolism, as discussed and illustrated in the present Part. The sister concept of product stereoselectivity will be presented in Part 8.
Chlojaponilactones B – E, Four New Lindenane Sesquiterpenoid Lactones from Chloranthus japonicus
Authors: Yan Huan , Li Xu‐Hong , Zheng Xue‐Fang , Sun Chang‐Li , Liu Hai‐Yang
Published: July 2013

Reinvestigation of the AcOEt‐soluble part of the EtOH extract of whole plants of Chloranthus japonicus afforded four new lindenane‐type sesquiterpenoid lactones, chlojaponilactones B–E (1–4, resp.), together with nine known sesquiterpenoids. Their structures and relative configurations were established on the basis of extensive spectroscopic data and by comparison with the relevant literature.
Psychosocial and lifestyle correlates of musculoskeletal pain patterns in adolescence: A 2‐year follow‐up study
Authors: Jussila L. , Paananen M. , Näyhä S. , Taimela S. , Tammelin T. , Auvinen J. , Karppinen J.
Published: July 2013

Background

The prevalence of musculoskeletal (MS) pain has been increasing among adolescents in the last decades. This may be related to either adverse changes in lifestyle and/or the psychosocial environment. Our study analysed the psychosocial and lifestyle correlates of musculoskeletal pain progression in adolescence.

Methods

The study was based on the 1986 Northern Finland Birth Cohort and included 1773 adolescents at the ages of 16 to 18. Latent class analysis was applied to find the homogeneous profiles of MS pains in four body areas (neck, shoulder, low back and limb). We analysed the associations between time spent in sedentary activities and sleeping, physical activity level, body mass index, alcohol consumption, smoking, and emotional and behavioural factors at 16 years, and belonging to pain clusters at 16 and 18 years.

Results

We found an association between a higher probability of MS pains between 16 and 18 years and increasing emotional and behavioural problems in both genders. Among boys, a high likelihood of MS pains during follow‐up was also associated with a long time spent sitting and insufficient sleeping time. Among girls, alcohol consumption associated with high pain probability. MS pains already co‐occur to a large extent in their early course.

Conclusions

The strong overlap of emotional and behavioural problems and MS pains in adolescence requires awareness in both research and clinical work.
Evaluation of In‐House Loop‐Mediated Isothermal Amplification (LAMP) Assay for Rapid Diagnosis of M. tuberculosis in Pulmonary Specimens
Authors: Sethi Sunil Kumar , Singh Sumeet , Dhatwalia Sunil Kumar , Yadav Rakesh , Mewara Abhishek , Singh Malkit , Tewari Rupinder , Sharma Meera
Published: July 2013

Background

Loop‐mediated isothermal amplification (LAMP) assay has come forward as a rapid, cost‐effective molecular technique for diagnosis of tuberculosis (TB) in developing countries. This study evaluated Mycobacterium tuberculosis–specific in‐house LAMP assay targeting 16s rRNA and compared it with other conventional tests and nucleic acid amplification assay (IS6110 PCR).

Methods

A total of 133 sputum specimens (103 from suspected pulmonary TB cases and 30 from non‐TB controls) were subjected to conventional tests, IS6110 PCR and 16s rRNA LAMP assay.

Results

Of the 103 patients, the maximum number of cases were found to be positive by LAMP assay, that is, in 87 (84.5%) patients, followed by culture positive in 78 (75.7%), IS6110 PCR in 74 (71.8%), and smear positive in 70 (67.9%) patients. Of the 83 smear positive and/or culture positive cases, LAMP detected 77 (92.77%) cases, and was found to be superior to IS6110 PCR, which could detect 69 (83.1%) cases; a concordance of 0.6 was obtained between the two tests using kappa statistics.

Conclusion

Overall, LAMP was simple and efficacious for early diagnosis of smear positive, culture positive cases as well as for confirmation of smear negative, culture negative cases, and was found to be superior to IS6110 PCR.
Brief Communication: Comparison the Diagnostic Performance of Four HBsAg ELISA Kits
Authors: Wan‐zhou Xu , Yan Li , Qing Wu , Ming Wang , Ze‐gang Wu
Published: July 2013

Background

Comparison of diagnostic efficiency of four ELISA kits for determining HBsAg.

Methods

Collecting 348 serum samples from clinical laboratory of Renmin Hospital of Wuhan University without specific gender and age requirements, determining HBsAg by the four ELISA kits, simultaneously. Confirmatory test was carried out when the initial results are positive.

Results

329 out of 348 samples results were consistent (94.5%), 152 out of 329 were positive, and 177 out of 329 were negative, and all the positive results can be confirmed; 19 samples were not consistent (5.5%), and only 1 sample was confirmed by the confirmatory test. After calculation, the diagnostic efficiencies of the four ELISA kits (Beijing Wantai, Xiamen Xinchuang, Zhuhai Lizhu, and Shanghai Kehua) were 98.6%, 98.0%, 99.7%, and 97.4%, respectively, the sensitivities were 100%, 99.4%, 99.4%, and 100%, respectively, the specificities were 97.5%, 96.9%, 100%, and 95.4%, respectively, the false positive rates were 2.5%, 3.1%, 0, and 4.6%, respectively, and the false negative rates were 0, 0.6%, 0.6%, and 0, respectively. All the initial absorbencies of the false positive samples were less than 1.0.

Conclusion

The diagnostic efficiency of Lizhu is the highest, while Kehua is the lowest. False positive or false negative results would take place in any of the kits, an HBsAg confirmatory test is essential for initially positive samples, especially with absorbance <1.0, because it can exclude most false positives.
A New Blood Collection Device Minimizes Cellular DNA Release During Sample Storage and Shipping When Compared to a Standard Device
Authors: Norton Sheila E. , Luna Kristin K. , Lechner Joel M. , Qin Jianbing , Fernando M. Rohan
Published: July 2013

Background

Cell‐free DNA (cfDNA) circulating in blood is currently used for noninvasive diagnostic and prognostic tests. Minimizing background DNA is vital for detection of low abundance cfDNA. We investigated whether a new blood collection device could reduce background levels of genomic DNA (gDNA) in plasma compared to K3EDTA tubes, when subjected to conditions that may occur during sample storage and shipping.

Methods

Blood samples were drawn from healthy donors into K3EDTA and Cell‐Free DNA™ BCT (BCT). To simulate shipping, samples were shaken or left unshaken. In a shipping study, samples were shipped or not shipped. To assess temperature variations, samples were incubated at 6°C, 22°C, and 37°C. In all cases, plasma was harvested by centrifugation and total plasma DNA (pDNA) assayed by quantitative real‐time polymerase chain reaction (qPCR).

Results

Shaking and shipping blood in K3EDTA tubes showed significant increases in pDNA, whereas no change was seen in BCTs. Blood in K3EDTA tubes incubated at 6°C, 22°C, and 37°C showed increases in pDNA while pDNA from BCTs remained stable.

Conclusions

BCTs prevent increases in gDNA levels that can occur during sample storage and shipping. This new device permits low abundance DNA target detection and allows accurate cfDNA concentrations.
Concomitant Oral and Intravenous Pharmacokinetics of Dabrafenib, a BRAF Inhibitor, in Patients with BRAF V600 Mutation‐Positive Solid Tumors
Authors: Denton Cathrine L. , Minthorn Elisabeth , Carson Stanley W. , Young Graeme C. , Richards‐Peterson Lauren E. , Botbyl Jeffrey , Han Chao , Morrison Royce A. , Blackman Samuel C. , Ouellet Daniele
Published: July 2013

Dabrafenib is an orally bioavailable, potent, and selective inhibitor of human wild‐type BRAF and CRAF kinases as well as mutant forms of BRAF kinase. The aim of this phase 1, single‐center, open‐label study in four patients with BRAF mutation‐positive solid tumors was to determine the absolute bioavailability of a 150 mg oral dose of dabrafenib. A microtracer study approach, in which a 50 µg radiolabeled intravenous (IV) microdose of dabrafenib was given concomitantly with a 150 mg oral dose, was used to simultaneously recover IV and oral pharmacokinetic parameters. The least squares mean (90% CI) absolute bioavailability of dabrafenib (HPMC capsules) was 94.5% (81.3%, 109.7%). Median Tmax after oral administration was 2.0 hours and the geometric mean terminal half‐life was 4.8 hours. The geometric mean clearance and volume of distribution after IV administration were 12.0 L/h and 45.5 L, respectively. Human clearance and volume of distribution at steady state were in agreement with predictions made using allometric scaling of pharmacokinetic parameters from four preclinical species. In conclusion, dabrafenib absolute bioavailability was high, whereas first‐pass metabolism was low. Furthermore, the microtracer approach provided an innovative and efficient method for assessing the absolute bioavailability of dabrafenib in patients with advanced cancer.