Evidence for bipolar jets in late stages of AGB winds

Bipolar expansion at various stages of evolution has been recently observed in a number of AGB stars. The expansion is driven by bipolar jets that emerge late in the evolution of AGB winds. The wind traps the jets, resulting in an expanding, elongated cocoon. Eventually the jets break-out from the confining spherical wind, as recently observed in W43A. This source displays the most advanced evolutionary stage of jets in AGB winds. The earliest example is IRC+10011, where the asymmetry is revealed in high-resolution near-IR imaging. In this source the jets turned on only ~200 years ago, while the spherical wind is ~4000 years old.Comment: 6 pages, to appear in "Asymmetrical Planetary Nebulae III" editors M. Meixner, J. Kastner, N. Soker, & B. Balick (ASP Conf. Series

An artificial CO-releasing metalloprotein built by histidine-selective metallation.

We report the design and synthesis of an aquacarbonyl Ru(II) dication cis-[Ru(CO)2(H2O)4](2+) reagent for histidine (His)-selective metallation of interleukin (IL)-8 at site 33. The artificial, non-toxic interleukin (IL)-8-Ru(II)(CO)2 metalloprotein retained IL-8-dependent neutrophil chemotactic activity and was shown to spontaneously release CO in live cells.We thank the European Commission (Marie Curie CIG to G.J.L.B., Marie Curie IEF to O.B.), FCT Portugal (FCT Investigator to G.J.L.B.) and the EPSRC for generous funding.This is the final published version. It first appeared at http://pubs.rsc.org/en/Content/ArticleLanding/2015/CC/c4cc10204e#!divAbstract

Effect of DMSO on Protein Structure and Interactions Assessed by Collision-Induced Dissociation and Unfolding

Given the frequent use of DMSO in biochemical and biophysical assays, it is desirable to understand the influence of DMSO concentration on the dissociation or unfolding behavior of proteins. In this study, the effects of DMSO on the structure and interactions of avidin and Mycobacterium tuberculosis (Mtb) CYP142A1 were assessed through collision-induced dissociation (CID) and collision-induced unfolding (CIU) as monitored by nanoelectrospray ionization–ion mobility–mass spectrometry (nESI-IM-MS). DMSO concentrations higher than 4% (v/v) destabilize the avidin tetramer toward dissociation and unfolding, via both its effects on charge state distribution (CSD) as well as at the level of individual charge states. In contrast, DMSO both protects against heme loss and increases the stability of CYP142A1 toward unfolding even up to 40% DMSO. Tandem MS/MS experiments showed that DMSO could modify the dissociation pathway of CYP142A1, while CIU revealed the protective effect of the heme group on the structure of CYP142A1.D.S.-H.C. acknowledges the Croucher Foundation and the Cambridge Commonwealth, European and International Trust for receipt of a Croucher Cambridge International Scholarship. M.E.K. was supported by a Commonwealth (University of Cambridge) Scholarship awarded in conjunc-tion with the Cambridge Commonwealth Trust and Cam-bridge Overseas Trust. K.J.M. and A.G.C. were supported by grants from the UK BBSRC (Biotechnology and Biological Sciences Research Council (BB/I019669/1 and BB/I019227/1)

Insight into Protein Conformation and Subcharging by DMSO from Native Ion Mobility Mass Spectrometry

Electrospray ionization-mass spectrometry (ESI-MS) interfaced with ion-mobility (IM) spectrometry has enabled the study of protein structure and interactions under native-like conditions. In biological assays, dimethyl sulfoxide (DMSO) is often included as a co-solvent to dissolve organic molecules. While low levels of DMSO are known to reduce the charge of protein ions generated by ESI, the exact mechanism by which this occurs has been debated. In this study, we describe the first application of IM–MS to study the effect of DMSO subcharging on native protein conformation. We find that at low concentrations, DMSO induces modest (1-2 %), but repeatable, reductions in protein collision-cross sections (CCSs) of four different protein complexes, avidin, concanavalin A, alcohol dehydrogenase, and pyruvate kinase, as measured by traveling-wave (TW) IM–MS. Individual protein charge states also experienced compaction in size, suggesting that this effect could not be attributed to the shift of charge state distribution by DMSO alone.D.S.-H. Chan acknowledges the support of the Croucher Foundation and the Cambridge Commonwealth, European and International Trust for receipt of a Croucher Cambridge International Scholarship

Efecto del injerto en las propiedades antioxidantes del tomate (Solanum lycopersicum L.)

The use of grafted plants in vegetable crop production is now being expanded greatly. However, few data are available on the nutritional composition of grafted vegetables with emphasis on antioxidant properties. Therefore, the major objective of this study was to evaluate antioxidant components of tomatoes influenced by grafting technique. The tomato plants were grown in a greenhouse located at Kriz˘evci, Croatia. The cultivars ‘Efialto’, ‘Heman’, and ‘Maxifort’ were used as rootstocks, while ‘Tamaris’ was used as scion. Grafting resulted in increase of number of marketable fruits per plant by 30%. Content of total vitamin C and total phenolics significantly decreased after grafting. The concentration of total extractable phenolics in tomatoes ranged from 287.1 to 977.4 mg gallic acid equivalents (GAE) kg–1 fresh weight, whereas lycopene content ranged from 11.44 to 60.99 mg kg–1 fresh weight. Antioxidant activities determined by 1,1-diphenyl-2 picrylhydrazyl (DPPH) method of grafts were significantly different compared to their respective rootstocks. The overall results showed that tomato grafting on suitable rootstocks has positive effects on the cultivation performance, but decreases nutritional quality of tomatoes. En la producción de cultivos hortícolas se está expandiendo actualmente de forma considerable el uso de plantas injertadas. Sin embargo, hay pocos datos disponibles sobre la composición nutricional de las hortícolas injertadas, especialmente sobre sus propiedades antioxidantes. El principal objetivo de este estudio fue evaluar los componentes antioxidantes de tomates influenciados por la técnica de injerto. Se cultivaron plantas de tomate en un invernadero de Kriz˘evcii, Croacia. Se utilizaron como portainjertos los cultivares ‘Efialto’, ‘Heman’, y ‘Maxifort’, mientras que ‘Tamaris’ fue utilizado como injerto. El resultado del injerto fue un aumento del 30% en el número de frutos comerciales por planta, mientras que el contenido de vitamina C y de fenoles totales disminuyó significativamente. La concentración del total de fenoles extraíbles en los tomates varió entre 287,1 y 977,4 mg de equivalentes de ácido gálico (GAE) por kilo sobre la base de peso fresco, mientras que el contenido de licopeno varió desde 11,44 hasta 60,99 mg kg–1 de peso fresco. Las actividades antioxidantes determinadas por el método DPPH (2,2-difenil-1-picrilhidrazilo) de los injertos fueron significativamente diferentes respecto de sus respectivos patrones. Los resultados globales muestran que el injerto de tomate sobre patrones adecuados tiene efectos positivos sobre el rendimiento de cultivo, pero la calidad nutricional de los frutos disminuye

Solvent content of protein crystals from diffraction intensities by Independent Component Analysis

An analysis of the protein content of several crystal forms of proteins has been performed. We apply a new numerical technique, the Independent Component Analysis (ICA), to determine the volume fraction of the asymmetric unit occupied by the protein. This technique requires only the crystallographic data of structure factors as input.Comment: 9 pages, 2 figures, 1 tabl

Mining 2:2 Complexes from 1:1 Stoichiometry: Formation of Cucurbit[8]uril−Diarylviologen Quaternary Complexes Favored by Electron-Donating Substituents

A 1:1 binding stoichiometry of a host−guest complex need not consist of a single host and guest. Diarylviologens containing electron-donating substituents complexed with cucurbit[8]uril (CB[8]) in a 1:1 stoichiometry exhibit abnormally large binding enthalpies compared to typical enthalpy changes observed for 1:1 binary complexes. Here, several CB[8]-mediated host−guest complexes, which were previously reported as 1:1 binary complexes, are verified to be 2:2 quaternary complexes by a combination of isothermal titration calorimetry, $^1$H, NOESY, and ROESY NMR, and ion mobility mass spectrometry, clearly indicating a binding motif of two partially overlapping diarylviologens held in place with two CB[8] molecules. Formation of 2:2 quaternary complexes is favored by electron-donating substituents, while electron-withdrawing substituents typically result in 1:1 binary complexes. The stacking of two highly conjugated diarylviologens in one quaternary motif affords the complexes enhanced conductance when considered as a single-molecular conductor. Moreover, an additional conducting signal previously observed for this “supramolecular” conductor can be readily understood with our 2:2 complexation model, corresponding to a parallel conductance pathway. Therefore, a 2:2 quaternary complex model grants a greater understanding of such supramolecular complexes, enabling the design of engineered, hierarchical structures and functional materials.The authors thank the Leverhulme Trust (project: ‘Natural material innovation for sustainable living’), the Marie Curie FP7 SASSYPOL ITN (607602) programme, and EPSRC (EP/ L504920/1) for funding

Revealing the sub-AU asymmetries of the inner dust rim in the disk around the Herbig Ae star R CrA

Models predict that in the innermost AU of the disk around Herbig Ae/Be star, the dust disk forms a "puffed-up" inner rim, which should result in a strongly asymmetric brightness distribution for disks seen under intermediate inclination. Using the VLTI/AMBER long-baseline interferometer, we obtained 24 near-infrared (H- and K-band) spectro-interferometric observations on the Herbig Ae star R CrA. In the derived visibility function, we detect the signatures of an extended (25 mas) and a compact component (5.8 mas), with the compact component contributing about 2/3 of the total flux. The brightness distribution is highly asymmetric, as indicated by the strong closure phases (up to 40 deg) and the detected position angle dependence of the visibilities and closure phases. To interpret these asymmetries, we employ geometric as well as physical models, including a binary model, a skewed ring model, and a puffed-up inner rim model with a vertical or curved rim shape. Our curved puffed-up rim model can reasonably well reproduce the interferometric observables and the SED simultaneously and suggests a luminosity of 29 L_sun and the presence of relatively large (> 1.2 micron) Silicate dust grains. Perpendicular to the disk, two bow shock-like structures appear in the associated reflection nebula NGC 6729, suggesting that the resolved sub-AU size disk is the driving engine of a large-scale outflow. Detecting, for the first time, strong non-localized asymmetries in the inner regions of a Herbig Ae disk, our study supports the existence of a puffed-up inner rim in YSO disks.Comment: 17 pages; 15 figures; Accepted by A&

Strong Near-Infrared Emission Interior to the Dust-Sublimation Radius of Young Stellar Objects MWC275 and AB Aur

Using the longest optical-interferometeric baselines currently available, we have detected strong near-infrared (NIR) emission from inside the dust-destruction radius of Herbig Ae stars MWC275 and AB Aur. Our sub-milli-arcsecond resolution observations unambiguously place the emission between the dust-destruction radius and the magnetospheric co-rotation radius. We argue that this new component corresponds to hot gas inside the dust-sublimation radius, confirming recent claims based on spectrally-resolved interferometry and dust evaporation front modeling.Comment: 12 pages, 4 figures, Accepted for publication in ApJ