Small-angle X-ray Diffraction Measurements Research Articles

Development of Low-Molecular-Weight Gelator/Polymer Composite Materials Utilizing the Gelation and Swelling Process of Polymeric Materials.

The creation of polymer composite materials by compositing fillers into polymer materials is an effective method of improving the properties of polymer materials, and the development of new fillers and their novel composite methods is expected to lead to the creation of new polymer composite materials. In this study, we develop a new filler material made of low-molecular-weight gelators by applying a gelation process that simultaneously performs the swelling (gelation) of crosslinked polymer materials and the self-assembly of low-molecular-weight gelators into low-dimensional crystals in organic solvents within polymer materials. The gelation process of crosslinking rubber-based polymers using alkylhydrazides/toluene as the low-molecular-weight gelator allowed us to composite self-assembled sheet-like crystals of alkylhydrazides as fillers in polymeric materials, as suggested by various microscopic observations, including infrared absorption measurements, small-angle X-ray diffraction measurements and thermal analysis, microscopy, and infrared absorption measurements. Furthermore, tensile tests of the composite materials demonstrated that the presence of fillers improved both the Young's modulus and the tensile strength, as well as the elongation at yield. Additionally, heat treatment was shown to facilitate filler dispersion and enhance the mechanical properties. The findings demonstrate the potential of self-assembled sheet-like crystals of low-molecular-weight gelators as novel filler materials for polymers. The study's composite method utilizing gelators via gelation proved effective.

In Situ and Ex Situ Studies of Ring-Like Assembly of Silica Nanoparticles in the Presence of Poly(propylene oxide)-Poly(ethylene oxide) Block Copolymers.

Block copolymer-mediated self-assembly of colloidal nanoparticles has attracted great attention for fabricating various nanoparticle arrays. We have previously shown that silica nanoparticles (SNPs) assemble into ring-like nanostructures in the presence of temperature-responsive block copolymers poly[(2-ethoxyethyl vinyl ether)-block-(2-methoxyethyl vinyl ether)] (PEOVE-PMOVE) in an aqueous phase. The ring-like nanostructures formed within an aggregate of PEOVE-PMOVE when the temperature was increased to 45 °C, at which the polymer is amphiphilic. Herein, we report that SNPs assemble into ring-like nanostructures even with a different temperature-responsive, amphiphilic block copolymer poly(propylene oxide)-block-poly(ethylene oxide) (PPO-PEO) at 45 °C. Field-emission scanning electron microscopy for SNP assemblies that were spin-coated on a substrate indicated that SNP first assembled into chain-like nanostructures and then bent into closed loops over several days. In contrast, in situ small-angle X-ray diffraction measurements revealed the formation of SNP nanorings within 75 s at 45 °C in the liquid phase. These results indicated that ring-like assembly of SNPs occurs quickly in the liquid phase, but the slow formation of Si-O-Si bonds between SNPs leads to their structure being destroyed by spin-coating. Intriguingly, SNPs with a diameter of 15 nm form a well-defined nanoring structure, with five SNPs located at the vertex points of a regular pentagon. Additionally, small-angle neutron scattering, where the contrast of the solvent (a mixture of H2O and D2O) matches that of SNPs, clarified that SNPs are contained within the spherical micelle formed from PPO-PEO. This work offers a facile and versatile approach to preparing ring-like arrays from inorganic colloidal nanoparticles, leading to applications including sensing, catalysis, and nanoelectronics.

Role and Effect of Meso-Structuring Surfactants on Properties and Formation Mechanism of Microfluidic-Enabled Mesoporous Silica Microspheres.

We have shown in a previous work that the combination of the emulsion solvent evaporation technique and droplet-based microfluidics allows for the synthesis of well-defined monodisperse mesoporous silica microcapsules (hollow microspheres), whose size, shape and composition may be finely and easily controlled. In this study, we focus on the crucial role played by the popular Pluronic® P123 surfactant, used for controlling the mesoporosity of synthesised silica microparticles. We show in particular, that although both types of initial precursor droplets, prepared with and without P123 meso-structuring agent, namely P123+ and P123- droplets, have a similar diameter (≃30 μm) and a similar TEOS silica precursor concentration (0.34 M), the resulting microparticles exhibit two noticeably different sizes and mass densities. Namely, 10 μm and 0.55 g/cm3 for P123+ microparticles, and 5.2 μm and 1.4 g/cm3 for P123- microparticles. To explain such differences, we used optical and scanning electron microscopies, small-angle X-ray diffraction and BET measurements to analyse structural properties of both types of microparticles and show that in the absence of Pluronic molecules, P123- microdroplets divide during their condensation process, on average, into three smaller droplets before condensing into silica solid microspheres with a smaller size and a higher mass density than those obtained in the presence of P123 surfactant molecules. Based on these results and on condensation kinetics analysis, we also propose an original mechanism for the formation of silica microspheres in the presence and in the absence of the meso-structuring and pore-forming P123 molecules.

MgADP Promotes Myosin Head Movement toward Actin at Low [Ca2+] to Increase Force Production and Ca2+-Sensitivity of Contraction in Permeabilized Porcine Myocardial Strips.

Myosin cross-bridges dissociate from actin following Mg2+-adenosine triphosphate (MgATP) binding. Myosin hydrolyses MgATP into inorganic phosphate (Pi) and Mg2+-adenosine diphosphate (ADP), and release of these hydrolysis products drives chemo-mechanical energy transitions within the cross-bridge cycle to power muscle contraction. Some forms of heart disease are associated with metabolic or enzymatic dysregulation of the MgATP-MgADP nucleotide pool, resulting in elevated cytosolic [MgADP] and impaired muscle relaxation. We investigated the mechanical and structural effects of increasing [MgADP] in permeabilized myocardial strips from porcine left ventricle samples. Sarcomere length was set to 2.0 µm at 28 °C, and all solutions contained 3% dextran T-500 to compress myofilament lattice spacing to near-physiological values. Under relaxing low [Ca2+] conditions (pCa 8.0, where pCa = -log10[Ca2+]), tension increased as [MgADP] increased from 0-5 mM. Complementary small-angle X-ray diffraction measurements show that the equatorial intensity ratio, I1,1/I1,0, also increased as [MgADP] increased from 0 to 5 mM, indicating myosin head movement away from the thick-filament backbone towards the thin-filament. Ca2+-activated force-pCa measurements show that Ca2+-sensitivity of contraction increased with 5 mM MgADP, compared to 0 mM MgADP. These data show that MgADP augments tension at low [Ca2+] and Ca2+-sensitivity of contraction, suggesting that MgADP destabilizes the quasi-helically ordered myosin OFF state, thereby shifting the cross-bridge population towards the disordered myosin ON state. Together, these results indicate that MgADP enhances the probability of cross-bridge binding to actin due to enhancement of both thick and thin filament-based activation mechanisms.

The effect of alkyl chain length of the imidazole ionic liquid surfactants on the improving lubricating properties of the hexagonal lyotropic liquid crystal composed of the [C16imCn]Br/hydrotalcite/H2O

The hydrotalcites were dispersed in the hexagonal lyotropic liquid crystals (LLCs) composed of 1-hexadecyl-3-alkyl imidazolium bromide ([C16imCn]Br, n = 1, 2 and 3) and H2O. The effects of the hydrotalcite concentration and the alkyl chain length of the [C16imCn]Br on the properties and the lubricant performance of the [C16imCn]Br/hydrotalcite hexagonal LLCs were studied by small angle X-ray diffraction measurements, rheology and tribology. Compared with the pure hexagonal LLCs, the incorporation of hydrotalcite into the [C16imCn]Br hexagonal LLCs can increase the interlayer distances and the viscoelasticity of the hybrid hexagonal LLCs gradually. However, the friction coefficient and wear volume decrease firstly and then increase with the increasing of hydrotalcite content. With the increase of the alkyl chain length of the [C16imCn]Br, the viscoelasticity, the interlayer distance and the water permeability of the mixed LLCs gradually increase which decreases the friction coefficient and wear volume at the moderate hydrotalcite content. The mechanism of the effective improvement of lubrication performance of the hybrid hexagonal LLCs is the tribofilm formed by the physical adsorption and tribochemical reaction of [C16imCn]Br/hydrotalcite LLCs on the steel surface.

Self-standing hollow porous AuPt nanospheres and their enhanced electrocatalytic performance

In this paper, we present a template method to fabricate AuPt hollow nanospheres by depositing Au inner layer and dendritic Pt outer layer onto PS template. The as-prepared AuPt hollow nanospheres can form self-standing hollow nanostructures under thermal treatment which is confirmed by small-angle X-ray scattering results. We believe that the self-standing structural features of them result from different thermal stability of Au and Pt elements. The small-angle X-ray diffraction measurements and X-ray photoelectron spectroscopy of binding energies certify the existing interaction between Au and Pt. It is suggested that Pt mole contents of AuPt hollow nanospheres can be varied by changing H2PtCl4 concentration during chemical deposition process. The methanol electrochemical oxidation reaction indicates these as-prepared AuPt hollow nanospheres possessing excellent potential applications on catalysts. Moreover, synthesis of multilayer hollow porous nanospheres such as Pt@Au@Pt proves that our method greatly enriches the species of the self-standing, hollow and porous functional nanomaterials.

Probing the effect of a room temperature ionic liquid on phospholipid membranes in multilamellar vesicles.

The large number of potential applications of ionic liquids (ILs) requires an understanding of their environmental impacts including their adverse effects on microorganisms living in soil and water. The molecular mechanism of toxic activities of these liquids is yet to be understood in detail. Any foreign molecules, interacting with an organism, have to encounter first the cellular membrane, which is predominantly composed of the lipid bilayer. In this work, multilamellar vesicles (MLV) of phospholipids have been used to shed light on the effect of an IL on the structure of a cellular membrane. The MLVs formed by the zwitterionic lipid, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) are found to shrink as a consequence of interaction with an imidazolium-based IL, 1-decyl-3-methylimidazolium tetrafluoroborate ([DMIM] [BF4]). The absorbed ILs significantly modify the surface charge of the MLVs. While these observations indicate a strong membrane-IL interaction, synchrotron-based small angle X-ray diffraction (SAXD) measurements provide a structural description of the interaction. SAXD and Fourier transform infrared spectroscopy studies clearly reveal a disordering effect of the IL on the conformational organization of the lipid chains. The presence of the negatively charged lipid 1,2-dipalmitoyl-sn-glycero-3-phospho-L-serine sodium salt (DPPS) in MLVs plays an important role in disordering the chains in the membrane and inter-bilayer interactions.

Peptide-based hydrogels with tunable nanostructures for the controlled release of dyes

Hydrogels with different microstructures including nanoribbons, stiff nanofibers, helical ribbons and nanotubes were observed by varying the concentration of oxidized glutathione (OGH) with a fixed concentration of sodium deoxycholate (SD). The self-assembled nanostructures were characterized in detail by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Random coil structures and β-sheets play important roles in the constructed nanostructures, which were verified by Fourier-transform infrared (FT-IR) spectroscopy and circular dichroism (CD), as well as small angle X-ray diffraction (SXRD) measurements. We proposed a mechanism for these nanostructural transformations. The "weak hydrogels" exhibited irreversible responses to heating and shaking and a reversible response to pH. Furthermore, the hydrogel could be used for the controlled release of dyes. Due to the strong electrostatic attraction between the positively charged dye methylene violet (MV) and the negatively charged nanofibers, methylene violet is released more slowly than the negatively charged dye, methyl orange (MO).

Discotic liquid crystals of transition metal complexes 56: Synthesis of mesogenic phthalocyanine-fullerene dyads and influence of the substitution position of alkoxy chains and the kind of terminal groups on appearance of the helical supramolecular structure

We have synthesized twelve novel discotic columnar liquid crystals based on a phenoxy-group-substituted phthalocyaninato copper(II) complex having the same alkoxy chain of C[Formula: see text]H[Formula: see text]O at different positions in the phenoxy group: the parent compounds {0a~0c-16}and the OH-substituted compounds {3a~3c-16}, the OFBA-substituted compounds {2a~2c-16}and the C[Formula: see text]-substituted dyads {1a~1c-16}. The letters of a, b and c mean substitution positions of C[Formula: see text]H[Formula: see text]O group at [Formula: see text], [Formula: see text] and [Formula: see text], respectively. We have investigated the influence of both substitution position of the alkoxy chains and the kind of terminal groups (OH, OFBA and C[Formula: see text] on the mesomorphism and the helical supramolecular structure, by using DSC, POM and temperature-variable small angle X-ray diffraction measurements. As a result, an additional big peak (Peak H) tends to appear at around 2[Formula: see text] = 1.1[Formula: see text] in the X-ray diffraction patterns only for the dyads {1a~1c-16}but not for the other compounds, {0a~0c-16}, {3a~3c-16}and {2a~2c-16}, regardless of the substitution positions of the alkoxy group. Moreover, we revealed that both the m-substituted derivative 1a-16 and the m,p-substituted derivative 1c-16 gave Peak H, but that only the p-substituted derivative 1b-16 did not give Peak H among these three dyads {1a~1c-16}. From the temperature-variable small angle X-ray diffraction measurements for the m,p-substituted derivative 1c-16 using two different sample preparation methods, we proved that the Peak H originates from a helical pitch of fullerenes. We also pointed out that the m-substituted long alkoxy chains are at least needed to form the helical supramolecular structure in the present (PhO)[Formula: see text]PcM-C[Formula: see text]-based dyads.

Effect of Self-Assembly of Oxalamide Based Organic Compounds on Melt Behavior, Nucleation, and Crystallization of Isotactic Polypropylene.

We report on the effect of an aliphatic oxalamide based nucleating agent (OXA3,6) on the melt and crystallization behavior of isotactic polypropylene (iPP) under defined shear conditions. Through polarized optical microscopy, we demonstrate that OXA3,6 self-assembles from the iPP melt into rhombic crystals whereas their size and distribution proved highly dependent on the employed cooling rates. The presence of 0.5 wt % of OXA3,6 in iPP results in a significant suppression in iPP melt viscosity, which could not be explained via molecular modeling. A possible cause for the drop in viscosity in the presence of OXA3,6 is attributed to the interaction (absorption) of high molecular weight iPP chains with the nucleating agent, thereby suppressing their contribution to the viscoelastic response of the melt. This proposed mechanism for the suppression in melt viscosity appears similar to that encountered by the homogeneous distribution of nanoparticles such as CNTs, graphene, and silica. Shear experiments, performed using a slit flow device combined with small-angle X-ray diffraction measurements, indicate that crystallization is significantly enhanced in the presence of OXA3,6 at relatively low shear rates despite its lowered sensitivity to shear. This enhancement in crystallization is attributed to the shear alignment of the rhombic OXA3,6 crystals that provide surface for iPP kebab growth upon cooling. Overall, the suppression in melt viscosity in combination with enhanced nucleation efficiency at low as well as high shear rates makes this self-assembling oxalamide based nucleating agent a promising candidate for fast processing.

Self-assembled 3DOM macro-/mesoporous TiO2 photoanode for dye-sensitized solar cells

Hierarchically structured TiO2 photo-anodes with ordered macropores and mesopores are prepared by two steps of self-assembling process. Scanning electron microscopy, transmission electron microscopy and small angle X-Ray diffraction measurements show that the samples were of 3D ordered macroporous structure and the ordered framework possessed numerous mesopores. In addition, the obtained TiO2 samples are systematically investigated by Ultraviolet-Visible spectrum, Brunauer-Emniett-Teller analysis. The Dye-Sensitized Solar Cells (DSCCs) fabricated with the 3D ordered macro-/mesoporous (3DOM/m) TiO2 photo-anode achieve a photoelectric conversion efficiency (PCE) of 9.20%, significantly higher than that of the DSSCs assembled with reference TiO2 photo-anodes without hierarchical structures. The enhanced PCE can be attributed to the unique morphology of 3DOM/m TiO2. This study demonstrates high potential of the TiO2 photoanode with hierarchical morphology for DSSC applications.

Fabrication of fluorescent star-like supramolecular materials through a novel ionic self-assembly strategy

Uniform star-like micro-scale materials were successfully fabricated by the complexation of a double tailed surfactant, sodium bis(2-ethyl-1-hexyl) sulfosuccinate (AOT), and a dye molecule, rhodamine B (RB), through a novel ionic self-assembly (ISA) route by using the seeds of RB. By using optical microscopy (OM), scanning electron microscopy (SEM), and small-angle X-ray diffraction (SAXD) measurements, morphology of such supramolecular materials was thoroughly investigated. The data from H NMR spectra indicated an equal molar ratio of AOT and RB in these star-like materials. The fluorescent properties of these ISA aggregates were studied through laser confocal scanning microscopy (LCSM) and fluorescence spectra. The formation of such star-like micromaterials was resulted from the delicate balance of various non-covalent interactions, including the electrostatic interactions, hydrophobic interactions, hydrogen bonding interactions as well as π-π stacking interactions, among which the electrostatic interactions between the head groups were regarded as the dominant force in promoting the supramolecular structure formation. To our best knowledge, this may be the first issue to fabricate such supramolecular structures through the ISA route with the aid of seeds from one building block.

Microfluidic-assisted Formation of Highly Monodisperse and Mesoporous Silica Soft Microcapsules

The fabrication of mesoporous silica microcapsules with a highly controlled particle size ranging in the micrometer size presents a major challenge in many academic and industrial research areas, such as for the developement of smart drug delivery systems with a well controlled loading and release of (bio)active molecules. Many studies based on the solvent evaporation or solvent diffusion methods have been developed during the last two decades in order to control the particle size, which is often found to range at a sub-micrometer scale. Droplet-based microfluidics proved during the last decade a powerful tool to produce highly monodisperse and mesoporous silica solid microspheres with a controllable size in the micrometer range. We show in the present study, in contrast with previous microfluidic-assisted approaches, that a better control of the diffusion of the silica precursor sol in a surrounding perfluorinated oil phase during the silica formation process allows for the formation of highly monodisperse mesoporous silica microcapsules with a diameter ranging in the 10 micrometer range. We show also, using optical, scanning and transmission electron microscopies, small angle x-ray diffraction and BET measurements, that the synthesized mesoporous silica microcapsules exhibit a soft-like thin shell with a thickness of about 1 μm, across which 5.9 nm sized mesopores form a well-ordered hexagonal 2D network. We suggest and validate experimentally a model where the formation of such microcapsules is controlled by the solvent evaporation process at the droplet-air interface.

Positron Annihilation Study of Porous ZnO Synthesized with Soft Template

Porous ZnO were synthesized with soft template method using zinc acetate Zn (CH3COO)2·2H2O as precursor and block copolymer F127 as the surfactant. Nitrogen adsorption-desorption measurements indicate that the ZnO sample contains large pores with mean diameter of about 30 nm. However, both small-angle X-ray diffraction and transmission electron microscope measurements indicate that the pore ordering is missing. Positron lifetime measurements reveal two long lifetime components in the porous ZnO. The longest lifetime τ4 (75 ns) corresponds to ortho-positronium (o-Ps) annihilation in large pores. The pore size estimated from τ4 is about 10.6 nm. This is much smaller than that estimated from Nitrogen adsorption-desorption measurements. In addition, the intensity I4 is only about 2.2%. This is probably due to the chemical quenching and/or inhibition of positronium formation induced by ZnO, which reduces o-Ps lifetime and intensity, and leads to under estimation of the pore size.

Structural characteristics of amorphous K-Bi citrate (De-Nol) and its aqueous solutions from EXAFS spectra

EXAFS (Extended X-ray Absorption Fine Structure) spectra of an amorphous solid Bi complex with citrate (known as De-Nol) and its aqueous solutions in a wide concentration range are measured. For the solutions good agreement is revealed between their structural parameters and the averaged interatomic distances and coordination numbers of the crystalline polymeric bismuth citrate compound composed of 12-nuclear Bi clusters based on the structure Bi12O22. So, it is found that droplets of the colloidal solution have a core structure close to the solid Bi12O22 cluster structure. When the concentrated solution is diluted the cluster structure is somewhat modified, it remaining similar to the structure of the Bi12O22 cluster and even at a tenfold dilution and the nearest (oxygen) spheres of the Bi environment changing insignificantly. The appearance in this case of an additional oxygen atom at a large distance from the bismuth atom likely due to the presence of the oxygen atom from the hydroxyl group of the diluted aqueous solution. The appearance of such oxygen is in accordance with particles size increase for diluted solution obtained by small-angle X-ray diffraction measurements. It is established that the structure of the amorphous solid complex is multiphase and, as a whole, similar to the structure of the solid binuclear complexes.

Knockdown of fast skeletal myosin-binding protein C in zebrafish results in a severe skeletal myopathy.

Myosin-binding protein C (MyBPC) in the muscle sarcomere interacts with several contractile and structural proteins. Mutations in the cardiac isoform (MyBPC-3) in humans, or animal knockout, are associated with cardiomyopathy. Function of the fast skeletal isoform (MyBPC-2) in living muscles is less understood. This question was addressed using zebrafish models, combining gene expression data with functional analysis of contractility and small-angle x-ray diffraction measurements of filament structure. Fast skeletal MyBPC-2B, the major isoform, was knocked down by >50% using morpholino antisense nucleotides. These morphants exhibited a skeletal myopathy with elevated apoptosis and up-regulation of factors associated with muscle protein degradation. Morphant muscles had shorter sarcomeres with a broader length distribution, shorter actin filaments, and a wider interfilament spacing compared with controls, suggesting that fast skeletal MyBPC has a role in sarcomere assembly. Active force was reduced more than expected from the decrease in muscle size, suggesting that MyBPC-2 is required for optimal force generation at the cross-bridge level. The maximal shortening velocity was significantly increased in the MyBPC-2 morphants, but when related to the sarcomere length, the difference was smaller, reflecting that the decrease in MyBPC-2B content and the resulting myopathy were accompanied by only a minor influence on filament shortening kinetics. In the controls, equatorial patterns from small-angle x-ray scattering revealed that comparatively few cross-bridges are attached (as evaluated by the intensity ratio of the 11 and 10 equatorial reflections) during active contraction. X-ray scattering data from relaxed and contracting morphants were not significantly different from those in controls. However, the increase in the 11:10 intensity ratio in rigor was lower compared with that in controls, possibly reflecting effects of MyBPC on the cross-bridge interactions. In conclusion, lack of MyBPC-2 results in a severe skeletal myopathy with structural changes and muscle weakness.

Titin strain contributes to the Frank–Starling law of the heart by structural rearrangements of both thin- and thick-filament proteins

The Frank-Starling mechanism of the heart is due, in part, to modulation of myofilament Ca(2+) sensitivity by sarcomere length (SL) [length-dependent activation (LDA)]. The molecular mechanism(s) that underlie LDA are unknown. Recent evidence has implicated the giant protein titin in this cellular process, possibly by positioning the myosin head closer to actin. To clarify the role of titin strain in LDA, we isolated myocardium from either WT or homozygous mutant (HM) rats that express a giant splice isoform of titin, and subjected the muscles to stretch from 2.0 to 2.4 μm of SL. Upon stretch, HM compared with WT muscles displayed reduced passive force, twitch force, and myofilament LDA. Time-resolved small-angle X-ray diffraction measurements of WT twitching muscles during diastole revealed stretch-induced increases in the intensity of myosin (M2 and M6) and troponin (Tn3) reflections, as well as a reduction in cross-bridge radial spacing. Independent fluorescent probe analyses in relaxed permeabilized myocytes corroborated these findings. X-ray electron density reconstruction revealed increased mass/ordering in both thick and thin filaments. The SL-dependent changes in structure observed in WT myocardium were absent in HM myocardium. Overall, our results reveal a correlation between titin strain and the Frank-Starling mechanism. The molecular basis underlying this phenomenon appears not to involve interfilament spacing or movement of myosin toward actin but, rather, sarcomere stretch-induced simultaneous structural rearrangements within both thin and thick filaments that correlate with titin strain and myofilament LDA.

Preparation of monodisperse Ni nanoparticles and their assembly into 3D nanoparticle superlattices

Monodisperse Ni nanoparticles with sizes varying from 4.8 to 11.3 nm are prepared via a one-pot reaction that involves the reduction of nickel(II) acetylacetonate in oleylamine in the presence of trioctylphosphine and 1,2-hexadecanediol. Reaction parameters such as temperature and the concentration of capping agent and metal precursor are critical for the adjustment of particle size. The decrease of crystallinity is observed for the samples with smaller particle sizes, which significantly affects the magnetic properties. Three-dimensional (3D) superlattices that are composed of Ni nanoparticles with different sizes are obtained on different substrates by a facile self-assembly process, and are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and small-angle X-ray diffraction (SAXRD). The Ni nanoparticle superlattices formed on carbon-coated TEM copper grids exhibit a dominant hexagonal close-packed (hcp) symmetry, although local fcc packing is also occasionally observed. The formation of 3D nanoparticle superlattice structures on Si substrates is confirmed from the SAXRD measurements. The method revealed in this study for the preparation of 3D superlattices composed of Ni nanoparticles with tunable sizes offers the potential to explore their interesting collective properties for multiple applications.

Familial Hypertrophic Cardiomyopathy-Linked Mutation (K104E) in the Myosin Regulatory Light Chain Affects Sarcomeric Structure and Function in Tg-Mice

Structural and functional effects of the familial hypertrophic cardiomyopathy (FHC)-linked mutation (Lysine 104-to-Glutamic Acid, K104E) in the human ventricular regulatory light chain (RLC) were studied in transgenic (Tg) mice. Small angle X-ray diffraction measurements on freshly skinned papillary muscle fibers demonstrated a mutation-induced increase in the interfilament lattice spacing at both short (2.3 µm) and long (2.5 µm) sarcomere lengths (SL) compared with Tg-WT. The intensity ratio (I1,1/I1,0) in WT fibers increased upon stretch (from SL=2.3 to SL=2.5 µm) indicating a shift in the cross-bridge mass distribution toward the thin filaments. In contrary, the K104E fibers demonstrated no change in I1,1/I1,0 on stretch. In line with X-ray data, K104E fibers developed higher passive tension at pCa 8 when consecutively stretched by 10%, 20%, 30% and 40% of their length compared to WT. Furthermore, the K104E mutation significantly decreased the endogenous RLC phosphorylation (∼2-fold) compared to WT myocardium. Histopathological changes included signs of hypertrophy and severe fibrotic lesions in Tg-K104E hearts. The higher mitochondrial content seen in the left ventricles of K104E mice by electron microscopy was supported by significantly increased myosin ATPase activity in Tg-K104E mice indicating higher energy demand and ATP consumption by the mutant hearts. Studies using single molecule detection demonstrated significantly decreased cross-bridge dissociation rates with lower duty cycle (indicative of lower force production) in Tg-K104E cardiac myofibrils compared to WT. Our results in Tg-K104E mice demonstrated cardiomyocyte hypertrophy and fibrosis, and significant alterations in sarcomere structure and function. Morphological abnormalities, increased passive stiffness and a slower cross bridge dissociation rate in Tg-K104E mice mirror the diastolic dysfunction phenotype observed in K104E positive patients. Supported by AHA12PRE12030412 (to WH), and NIH HL-071778 and HL-108343 (to DSC).

One-step synthesis of a highly homogeneous SBA–NHC hybrid material: en route to single-site NHC–metal heterogeneous catalysts with high loadings

The one-step synthesis of a mesoporous silica of SBA type, functionalized with a 1-(2,6-diisopropylphenyl)-3-propyl-imidazolium (iPr2Ar-NHC-propyl) cation located in the pore channels, is described. This material was obtained by the direct hydrolysis and co-condensation of tetraethylorthosilicate (TEOS) and 1-(2,6-diisopropylphenyl)-3-[3-(triethoxysilyl)propyl]-imidazolium iodide in the presence of Pluronic P123 as a non-ionic structure-directing agent and aqueous HCl (37%) as an acid catalyst. Small-angle X-ray diffraction measurements, scanning and transmission electron microscopies, as well as dinitrogen sorption analyses revealed that the synthesized material is highly mesoporous with a 2D hexagonal arrangement of the porous network. (13)C and (29)Si CP-MAS NMR spectroscopy confirmed that the material contains intact iPr2Ar-NHC-propyl cations, which are covalently anchored via silicon atoms fused into the silica matrix. Moreover, comparison of the latter data with those of an analogous post-synthetic grafted SBA-NHC material allowed us to establish that, as expected, (i) it is most probably more homogeneous and (ii) it shows a more robust anchoring of the organic units. Finally, elemental mapping by energy dispersive X-ray spectroscopy in the scanning electron microscope demonstrated a very homogeneous distribution of the imidazolium units within the one-pot material, moreover with a high content. This study thus demonstrates that a relatively bulky and hydrophilic imidazolium unit can be directly co-condensed with TEOS in the presence of a structure-directing agent to provide in a single step a highly ordered and homogeneous mesoporous hybrid SBA-NHC material, possessing a significant number of cationic NHC sites.