A Deep Dive into VDAC1 Conformational Diversity Using All-Atom Simulations Provides New Insights into the Structural Origin of the Closed States

The voltage-dependent anion channel 1 (VDAC1) is a crucial mitochondrial transporter that controls the flow of ions and respiratory metabolites entering or exiting mitochondria. As a voltage-gated channel, VDAC1 can switch between a high-conducting “open” state and a low-conducting “closed” state emerging at high transmembrane (TM) potentials. Although cell homeostasis depends on channel gating to regulate the transport of ions and metabolites, structural hallmarks characterizing the closed states remain unknown. Here, we performed microsecond accelerated molecular dynamics to highlight a vast region of VDAC1 conformational landscape accessible at typical voltages known to promote closure. Conformers exhibiting durable subconducting properties inherent to closed states were identified. In all cases, the low conductance was due to the particular positioning of an unfolded part of the N-terminus, which obstructed the channel pore. While the N-terminal tail was found to be sensitive to voltage orientation, our models suggest that stable low-conducting states of VDAC1 predominantly take place from disordered events and do not result from the displacement of a voltage sensor or a significant change in the pore. In addition, our results were consistent with conductance jumps observed experimentally and corroborated a recent study describing entropy as a key factor for VDAC gating.     

Effect of freezing treatments and yeast amount on sensory and physical properties of sweet bakery products

The frozen bakery market has grown significantly in developed countries over the past decade.     

Variation of MUF and PMUF resins mass fractions during preparation

The variation of molecular mass distribution with the progress of the reaction was studied for the following: (i) sequential‐type melamine–urea–formaldehyde (MUF) resin formulations in which the sequence of addition of chemicals follows well‐defined species reactivity principles; (ii) a nonsequential MUF formulation in which simultaneous melamine and urea competition for formaldehyde yields a MF resin cocondensed with small amounts of urea. This resin became soaked with reacted and unreacted monomeric urea species. (iii) A PMUF resin, namely a MUF resin with a small proportion of phenol (7.8% by weight on melamine and urea) cocondensed with the main MUF fraction. All the formulations used were industrial resins formulations in current use. Development and variation of molecular mass fractions, from which performance and other useful resin parameters depend, have been found to depend on the type of resin formulation used for these type of aminoplastic resins. The two very different MUF resin formulations yielded different variations in molecular mass fractions during the progress of the reaction and during the so‐called ambient temperature “maturing” of the resin. The PMUF resin also showed both similar and different fractions present during manufacturing and during short term ageing at ambient temperature. While similarities in recurrent fractions and in trends are common to all the three different formulations, differences between them are also clearly observed. A major proportion of the reaction of some of the aminoplastic resins examined also occurs on ageing (i.e.“maturing” of the resin at ambient temperature), this appearing to be an essential phase of the resin preparation process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4842–4855, 2006     

Ester acceleration mechanisms in phenol–formaldehyde resin adhesives

An analysis of phenol–formaldehyde (PF) resins obtained by the addition of 0.5–5% glycerol triacetate (triacetin) as an accelerator during resin preparation showed the presence of intermediates involved in the acceleration mechanism. ¹³C-NMR spectroscopy, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectroscopy (MS), and gel permeation chromatography allowed us to identify some of the intermediates left over in the PF resin itself. The permanence in the resin of these labile intermediates, not easily observed otherwise, appeared to be due to the reaching of the diffusion-controlled phase of the reaction. The mechanism involved appeared considerably more complex and different from any of the mechanisms presented previously. As a consequence of the evident complexity of the mechanism, it was not really possible to advance a complete mechanism of the reaction nor determine the real cause of the increase in the strength of the final network. The mechanism involved the phenate ion of the resin to apparently give a carbonyl or carboxyl group attached to the aromatic ring. Either directly or by subsequent rapid rearrangement after the initial attack, these CO groups were found on sites different from the ortho position. The appearance gathered from NMR shift calculation indicated preferential positioning or repositioning to the para site and, surprisingly, to the meta sites of the phenolic ring. The shifts of these CO groups correspond to those of an anhydride and to no other intermediate structures previously thought of. Anhydride-like bridges were clearly shown by MALDI-TOF MS to contribute to oligomer structures in which linkages between phenol rings were mixed methylene bridges and anhydride bridges. These structures appeared to be temporary, possibly due to the instability of the anhydride bridges; hence, they were in small proportions at any given moment of the reaction. MALDI-TOF analysis clearly indicated that these structures were at some moment an integral part of the structure of the liquid resin and that they existed parallel to the methylene bridges pertaining to a normal PF resin structure. Previous spectra showed that similar but not identical intermediates were present also in organic and inorganic catalyzed PF resins. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:3075–3093, 2006     

Plant Chemical Defense Induced by a Seed-Eating Pollinator Mutualist

Plant-seed parasite pollination mutualisms involve a specific pollinator whose larvae develop by consuming a fraction of the host plant seeds. These mutualisms are stable only if the plant can control seed destruction by the larvae. Here, we studied the chemical response of the European globeflower Trollius europaeus to infestation by an increasing number of Chiastocheta fly larvae. We used liquid chromatographic analysis to compare the content of phenolic compounds in unparasitized and parasitized fruits collected in two natural populations of the French Alps, and mass spectrometry and nuclear magnetic resonance to elucidate the structure of adonivernith, a C-glycosyl-flavone. This compound is present in many of the organs of T. europaeus, but not found in other Trollius species. Furthermore, it is overproduced in the carpel walls of parasitized fruits, and this induced response to infestation by fly larvae is density-dependent (increases with larval number), and site-dependent (more pronounced in the high-altitude site). Mechanical damage did not induce adonivernith production. This tissue-specific and density-dependent response of T. europaeus to infestation by Chiastocheta larvae might be an efficient regulation mechanism of seed-predator mutualist population growth if it decreases survival or growth of the larvae.     

Non-toxic, zero emission tannin-glyoxal adhesives for wood panels

In this study different tannin-glyoxal glue mixes for particleboard were studied. Gel times at 100 °C of 45% water solutions of commercial pine tannin extract (Pinus radiata ex Diteco Ltda, Chile) with respectively 8% paraformaldehyde and 9% glyoxal were done at different pHs. Duplicate one layer laboratory particleboards were prepared by adding 12% total resin solids of adhesives composed of commercial pine tannin extract (Pinus radiata ex Diteco Ltda, Chile) with paraformaldehyde, or glyoxal or polymeric 4,4’ diphenylmethanne diisocianate (pMDI), respectively. It was found that tannin-glyoxal panels which do not contain formaldehyde and with an emission equal to that of unbounded wood can be obtained by the use of glyoxal as hardener.     

Comparative 13C‐NMR and matrix‐assisted laser desorption/ionization time‐of‐flight analyses of species variation and structure maintenance during melamine–urea–formaldehyde resin preparation

The preparation of an industrially used sequential formulation of a melamine–urea–formaldehyde resin was followed by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry and ¹³C‐NMR analysis. The analysis allowed us to identify and follow the appearance, increase, decrease, and disappearance of a multitude of chemical species during the preparation of both the initial urea–formaldehyde (UF) phase of the reaction and the subsequent reaction of melamine with the UF resin that formed. The analysis indicated that (1) the increase and decrease in the species that formed proceeded through a cycle of the formation and degradation of species occurring continuously through what appeared to be a series of complex equilibria, (2) even at the end of the reaction a predominant proportion of methylene ether bridges was still present, (3) some small proportion of methylene bridges already had formed in the UF reaction phase of the resin even under rather alkaline conditions, and (4) the addition of melamine to the UF prepolymer induced some noticeable rearrangement of methylene ether bridges to methylene bridges. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Wood preservation by a mixed anhydride treatment: A 13C‐NMR investigation of simple models of polymeric wood constituents

The treatment of wood by a mixed aceto/oleic (or other fatty acid residue) anhydride promoted as a safe and environmentally friendly wood preservation system was examined quantitatively by liquid‐phase ¹³C‐NMR and solid‐phase magic angle spinning–DEC (proton decoupling) ¹³C‐NMR through of all its different stages to determine which reactions occurred with simple model compounds of the polymeric constituents of wood. The preparation of the mixed aceto/oleic anhydride under different conditions was also undertaken. The anhydride formed, but its percentage yield was only 30%. The mix composed of unreacted acetic anhydride, the mixed aceto/oleic anhydride, and a large proportion of free acetic and oleic acid, which are used for wood preservation, yielded the acetylation of the lignin model compound (1) by the reaction of the acetic anhydride with it and (2) by the reaction of the acetic part of the mixed anhydride. In this reaction, all of the mixed anhydride was consumed. The oleic part of the mixed anhydride was unable to form esters with either lignin or wood holocellulose as it was far less reactive than the acetic part. Some acetylation of holocellulose occurred, and some traces of its oleic acid ester also occurred under some conditions. This system of treatment through a mixed anhydride appeared to consist of just an acetylation with acetic anhydride mixed with some oleic acid as a water repellent, both of which are already known processes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009