A Flavone-Based Solvatochromic Probe with A Low Expected Perturbation Impact on the Membrane Physical State

The study of the cell membrane is an ambitious and arduous objective since its physical state is regulated by a series of processes that guarantee its regular functionality. Among the different methods of analysis, fluorescence spectroscopy is a technique of election, non-invasive, and easy to use. Besides, molecular dynamics analysis (MD) on model membranes provides useful information on the possibility of using a new probe, following its positioning in the membrane, and evaluating the possible perturbation of the double layer. In this work, we report the rational design and the synthesis of a new fluorescent solvatochromic probe and its characterization in model membranes. The probe consists of a fluorescent aromatic nucleus of a 3-hydroxyflavone moiety, provided with a saturated chain of 18 carbon atoms and a zwitterionic head so to facilitate the anchoring to the polar heads of the lipid bilayer and avoid the complete internalization. It was possible to study the behavior of the probe in GUV model membranes by MD analysis and fluorescence microscopy, demonstrating that the new probe can efficiently be incorporated in the lipid bilayer, and give a color response, thanks to is solvatochromic properties. Moreover, MD simulation of the probe in the membrane supports the hypothesis of a reduced perturbation of the membrane physical state.

Fusing Carbocycles of Inequivalent Ring Size to a Bis(imino)pyridine-Iron Ethylene Polymerization Catalyst: Distinctive Effects on Activity, PE Molecular Weight, and Dispersity

The 4,6-bis(arylimino)-1,2,3,7,8,9,10-heptahydrocyclohepta[b]quinoline-iron(II) chlorides (aryl = 2,6-Me2C6H3Fe1; 2,6-Et2C6H3Fe2; 2,6-i-Pr2C6H3Fe3; 2,4,6-Me3C6H2Fe4; and 2,6-Et2-4-Me2C6H2Fe5) have been prepared in good yield by a straightforward one-pot reaction of 2,3,7,8,9,10-hexahydro-1H-cyclohepta[b]quinoline-4,6-dione, FeCl2·4H2O, and the appropriate aniline in acetic acid. All ferrous complexes have been characterized by elemental analysis and FT-IR spectroscopy. In addition, the structure of Fe3 has been determined by single crystal X-ray diffraction, which showed the iron center to adopt a distorted square pyramidal geometry with the saturated sections of the fused six- and seven-membered carbocycles to be cis-configured. In combination with either MAO or MMAO, Fe1–Fe5 exhibited exceptionally high activities for ethylene polymerization (up to 15.86×106 gPE mol−1 Fe h−1 at 40°C (MMAO) and 9.60×106 gPE mol−1 Fe h−1 at 60°C (MAO)) and produced highly linear polyethylene (HLPE, Tm≥128°C) with a wide range in molecular weights; in general, the MMAO-promoted polymerizations were more active. Irrespective of the cocatalyst employed, the 2,6-Me2-substituted Fe1 and Fe4 proved the most active while the more sterically hindered 2,6-i-Pr2Fe3 the least but afforded the highest molecular weight polyethylene (Mw: 65.6–72.6 kg mol-1). Multinuclear NMR spectroscopic analysis of the polymer formed using Fe4/MMAO at 40°C showed a preference for fully saturated chain ends with a broad bimodal distribution a feature of the GPC trace (Mw/Mn=13.4). By contrast, using Fe4/MAO at 60°C a vinyl-terminated polymer of lower molecular weight (Mw=14.2 kg mol−1) was identified that exhibited a unimodal distribution (Mw/Mn=3.8). Moreover, the amount of aluminoxane cocatalyst employed, temperature, and run time were also found to be influential on the modality of the polymer.

FINITELY VALUATIVE DOMAINS

For a pair of rings S ⊆ T and a nonnegative integer n, an element t ∈ T\S is said to be within n steps of S if there is a saturated chain of rings S = S0 ⊊ S1 ⊊ ⋯ ⊊ Sm = S[t] with length m ≤ n. An integral domain R is said to be n-valuative (respectively, finitely valuative) if for each nonzero element u in its quotient field, at least one of u and u-1 is within n (respectively, finitely many) steps of R. The integral closure of a finitely valuative domain is a Prüfer domain. Moreover, an n-valuative domain has at most 2n + 1 maximal ideals; and an n-valuative domain with 2n + 1 maximal ideals must be a Prüfer domain.

Fatty Acid Remodeling of GPI-anchored Proteins Is Required for Their Raft Association

Whereas most of the cellular phosphatidylinositol (PI) contain unsaturated fatty chains and are excluded from rafts, GPI-anchored proteins (APs) unusually contain two saturated fatty chains in their PI moiety, and they are typically found within lipid rafts. However, the origin of the saturated chains and whether they are essential for raft association are unclear. Here, we report that GPI-APs, with two saturated fatty chains, are generated from those bearing an unsaturated chain by fatty acid remodeling that occurs most likely in the Golgi and requires post-GPI-attachment to proteins (PGAP)2 and PGAP3. The surface GPI-APs isolated from the PGAP2 and -3 double-mutant Chinese hamster ovary (CHO) cells had unsaturated chains, such as oleic, arachidonic, and docosatetraenoic acids in the sn-2 position, whereas those from wild-type CHO cells had exclusively stearic acid, a saturated chain, indicating that the sn-2 chain is exchanged to a saturated chain. We then assessed the association of GPI-APs with lipid rafts. Recovery of unremodeled GPI-APs from the double-mutant cells in the detergent-resistant membrane fraction was very low, indicating that GPI-APs become competent to be incorporated into lipid rafts by PGAP3- and PGAP2-mediated fatty acid remodeling. We also show that the remodeling requires the preceding PGAP1-mediated deacylation from inositol of GPI-APs in the endoplasmic reticulum.

Structures of mono-unsaturated triacylglycerols. II. The β2 polymorph

An improved crystal structure model has been established for the β2 polymorph of the symmetric mono-unsaturated triacylglycerol 1,3-distearoyl-2-oleoylglycerol (SOS) and the equivalent β-V polymorph of Ivory Coast cocoa butter. In addition, the crystal structures of the β2 polymorphs are reported for the triacylglycerols 1,3-dipalmitoyl-2-oleoylglycerol (POP) and 1-palmitoyl-2-oleoyl-3-stearoylglycerol (POS), which are, together with SOS, the major components of cocoa butter, and that of 1-stearoyl-2-oleoyl-3-arachidoylglycerol (SOA). The existence of β2-POS and β2-SOA has not been previously reported in the literature. All structures have been solved from high-resolution laboratory or synchrotron powder diffraction data with the direct-space parallel-tempering program FOX and refined with the Rietveld module of GSAS. All compounds crystallize in similar monoclinic unit cells (Cc) with very long b axes (> 127 Å). The oleic chains are packed together and sandwiched between saturated chain layers, forming acyl-chain three-packs. An analysis of the β2 polymorphs and β1 polymorphs [van Mechelen et al. (2006). Acta Cryst. B62, 1121–1130] shows that they contain the same three-packs and differ only in the symmetry relation between the three-packs. The three-pack build-up provides an explanation of the mechanism of the phase transition that causes the formation of fat bloom on dark chocolate.

Structures of mono-unsaturated triacylglycerols. I. The β1 polymorph

The crystal structures of the β1 polymorphs of mono-unsaturated triacylglycerols have been solved from high-resolution laboratory and synchrotron powder diffraction data for five pure compounds, the 1,3-dimyristoyl-2-oleoylglycerol (β1-MOM), 1,3-dipalmitoyl-2-oleoylglycerol (β1-POP), 1,3-distearoyl-2-oleoylglycerol (β1-SOS), 1-palmitoyl-2-oleoyl-3-stearoylglycerol (β1-POS), 1-stearoyl-2-oleoyl-3-arachidoylglycerol (β1-SOA) and three mixtures: the co-crystallized 1:1 molar mixture of SOS and POP [β1-SOS/POP (1:1)] and two cocoa butters from Bahia and Ivory Coast, both in their β-VI (= β1) polymorph. All eight β1 structures crystallized in the space group (P21/n) and have two short cell axes (5.44–5.46 and 8.18–8.22 Å), as well as a very long b axis (112–135 Å). The dominant-zone problem in the indexing of the powder patterns was solved with the special brute-force indexing routine LSQDETC from the POWSIM program. Structures were solved using the direct-space parallel-tempering method FOX and refined with GSAS. Along the b axis, alternations of inversion-centre-related `three-packs' can be discerned. Each `three-pack' has a central oleic zone, with oleic acyl chains of the molecules being packed together, that is sandwiched between two saturated-chain zones. The conformation of the triacylglycerol molecules is relatively `flat' because the least-square planes through the saturated chains and those through the saturated parts of the olein chain are parallel. The solution of the β1 structures is a step forward towards understanding the mechanism of fat-bloom formation in dark chocolate and has led to a reexamination of the β2 structural model [see van Mechelen et al. (2006). Acta Cryst. B62, 1131–1138].

Saturated chain partitions in ranked partially ordered sets, and non-monotone symmetric 11-Venn diagrams

In this paper we show that there are at least 2110 non-isomorphic 11-doilies, that is, there are many non-isomorphic symmetric, non-simple, non-monotone 11-Venn diagrams, with "many" vertices. We do not achieve the maximum vertex set size, 2046, but we approach it closely, improving from the previous 462 in [10] to 1837. The doilies constructed here cannot be constructed by either of the methods of [10] or [6]. The main purpose of this paper is not to publish these attractive diagrams but to inspire new studies by raising ideas, methods, questions, and conjectures, hoping for results analogous to those generated in [10]. These ideas connect two seemingly distant areas of mathematics: a special area of combinatorial geometry, namely, certain families of simple closed Jordan curves in the plane, and the study of ranked partially ordered sets or posets.