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Crystal structure of diethyl (E)-2-[(benzofuran-2-yl)methylidene]succinate
2015, Schirmer, Marie-Luis, Spannenberg, Anke, Werner, Thomas
The title compound, C17H18O5, was synthesized by a base-free catalytic Wittig reaction. The molecule consists of a diethyl itaconate unit, which is connected via the C=C double bond to a benzofuran moiety. The benzofuran ring system (r.m.s. deviation = 0.007 Å) forms dihedral angles of 79.58 (4) and 12.12 (10)° with the mean planes through the cis and trans ethoxycarbonyl groups, respectively. An intramolecular C-H...O hydrogen bond involving the O atom of the benzofuran moiety is observed. In the crystal, molecules are linked into ribbons running parallel to the b axis by C-H...O hydrogen bonds.
Fast, Label-Free Tracking of Single Viruses and Weakly Scattering Nanoparticles in a Nanofluidic Optical Fiber
2015, Faez, Sanli, Lahini, Yoav, Weidlich, Stefan, Garmann, Rees F., Wondraczek, Katrin, Zeisberger, Matthias, Schmidt, Markus A., Orrit, Michel, Manoharan, Vinothan N.
High-speed tracking of single particles is a gateway to understanding physical, chemical, and biological processes at the nanoscale. It is also a major experimental challenge, particularly for small, nanometer-scale particles. Although methods such as confocal or fluorescence microscopy offer both high spatial resolution and high signal-to-background ratios, the fluorescence emission lifetime limits the measurement speed, while photobleaching and thermal diffusion limit the duration of measurements. Here we present a tracking method based on elastic light scattering that enables long-duration measurements of nanoparticle dynamics at rates of thousands of frames per second. We contain the particles within a single-mode silica fiber having a subwavelength, nanofluidic channel and illuminate them using the fiber's strongly confined optical mode. The diffusing particles in this cylindrical geometry are continuously illuminated inside the collection focal plane. We show that the method can track unlabeled dielectric particles as small as 20 nm as well as individual cowpea chlorotic mottle virus (CCMV) virions-26 nm in size and 4.6 megadaltons in mass-at rates of over 3 kHz for durations of tens of seconds. Our setup is easily incorporated into common optical microscopes and extends their detection range to nanometer-scale particles and macromolecules. The ease-of-use and performance of this technique support its potential for widespread applications in medical diagnostics and micro total analysis systems.
Mechanical Robustness of Graphene on Flexible Transparent Substrates
2016, Kang, Moon H., Prieto López, Lizbeth O., Chen, Bingan, Teo, Ken, Williams, John A., Milne, William I., Cole, Matthew T.
This study reports on a facile and widely applicable method of transferring chemical vapor deposited (CVD) graphene uniformly onto optically transparent and mechanically flexible substrates using commercially available, low-cost ultraviolet adhesive (UVA) and hot-press lamination (HPL). We report on the adhesion potential between the graphene and the substrate, and we compare these findings with those of the more commonly used cast polymer handler transfer processes. Graphene transferred with the two proposed methods showed lower surface energy and displayed a higher degree of adhesion (UVA: 4.40 ± 1.09 N/m, HPL: 0.60 ± 0.26 N/m) compared to equivalent CVD-graphene transferred using conventional poly(methyl methacrylate) (PMMA: 0.44 ± 0.06 N/m). The mechanical robustness of the transferred graphene was investigated by measuring the differential resistance as a function of bend angle and repeated bend–relax cycles across a range of bend radii. At a bend angle of 100° and a 2.5 mm bend radius, for both transfer techniques, the normalized resistance of graphene transferred on polyethylene terephthalate (PET) was around 80 times less than that of indium–tin oxide on PET. After 104 bend cycles, the resistance of the transferred graphene on PET using UVA and HPL was found to be, on average, around 25.5 and 8.1% higher than that of PMMA-transferred graphene, indicating that UVA- and HPL-transferred graphene are more strongly adhered compared to PMMA-transferred graphene. The robustness, in terms of maintained electrical performance upon mechanical fatigue, of the transferred graphene was around 60 times improved over ITO/PET upon many thousands of repeated bending stress cycles. On the basis of present production methods, the development of the next-generation of highly conformal, diverse form factor electronics, exploiting the emerging family of two-dimensional materials, necessitates the development of simple, low-cost, and mechanically robust transfer processes; the developed UVA and HPL approaches show significant potential and allow for large-area-compatible, near-room temperature transfer of graphene onto a diverse range of polymeric supports.
Crystal structure of bis{μ2-[(2-iminocyclopentylidene)methylidene]azanido-κ2 N:N'}bis[(η5-pentamethylcyclopentadienyl)zirconium(IV)] hexane monosolvate
2015, Becker, Lisanne, Spannenberg, Anke, Arndt, Perdita, Rosenthal, Uwe
The title compound, [Zr2(C10H15)4(C6H6N2)2]·C6H14, was obtained by the stoichiometric reaction of adiponitrile with [Zr(C10H15)2([eta]2-Me3SiC2SiMe3)]. Intramolecular nitrile-nitrile couplings and deprotonation of the substrate produced the (1-imino-2-enimino)cyclopentane ligand, which functions as a five-membered bridge between the two metal atoms. The ZrIV atom exhibits a distorted tetrahedral coordination sphere defined by two pentamethylcyclopentadienyl ligands, by the imino unit of one (1-imino-2-enimino)cyclopentane and by the enimino unit of the second (1-imino-2-enimino)cyclopentane. The cyclopentane ring of the ligand shows an envelope conformation. The asymmetric unit contains one half of the complex and one half of the hexane solvent molecule, both being completed by the application of inversion symmetry. One of the pentamethylcyclopentadienyl ligands is disordered over two sets of sites with a refined occupancy ratio of 0.8111 (3):0.189 (3). In the crystal, the complex molecules are packed into rods extending along [100], with the solvent molecules located in between. The rods are arranged in a distorted hexagonal packing.
Structure-property relationships in nanoporous metallic glasses
2016, Şopu, D., Soyarslan, C., Sarac, B., Bargmann, S., Stoica, M., Eckert, J.
We investigate the influence of various critical structural aspects such as pore density, distribution, size and number on the deformation behavior of nanoporous Cu64 Zr36 glass. By using molecular dynamics and finite element simulations an effective strategy to control the strain localization in nanoporous heterostructures is provided. Depending on the pore distribution in the heterostructure, upon tensile loading the nanoporous glass showed a clear transition from a catastrophic fracture to localized deformation in one dominant shear band, and ultimately to homogeneous plastic flow mediated by a pattern of multiple shear bands. The change in the fracture mechanism from a shear band slip to necking-like homogeneous flow is quantitative interpreted by calculating the critical shear band length. Finally, we identify the most effective heterostructure with enhanced ductility as compared to the monolithic bulk metallic glass. The heterostructure with a fraction of pores of about 3% distributed in such a way that the pores do not align along the maximum shear stress direction shows higher plasticity while retaining almost the same strength as the monolithic glass. Our results provide clear evidence that the mechanical properties of nanoporous glassy materials can be tailored by carefully controlling the design parameters.
Protein-Assisted Assembly of Modular 3D Plasmonic Raspberry-like Core/Satellite Nanoclusters: Correlation of Structure and Optical Properties
2016, Höller, Roland P. M., Dulle, Martin, Thomä, Sabrina, Mayer, Martin, Steiner, Anja Maria, Förster, Stephan, Fery, Andreas, Kuttner, Christian, Chanana, Munish
We present a bottom-up assembly route for a large-scale organization of plasmonic nanoparticles (NPs) into three-dimensional (3D) modular assemblies with core/satellite structure. The protein-assisted assembly of small spherical gold or silver NPs with a hydrophilic protein shell (as satellites) onto larger metal NPs (as cores) offers high modularity in sizes and composition at high satellite coverage (close to the jamming limit). The resulting dispersions of metal/metal nanoclusters exhibit high colloidal stability and therefore allow for high concentrations and a precise characterization of the nanocluster architecture in dispersion by small-angle X-ray scattering (SAXS). Strong near-field coupling between the building blocks results in distinct regimes of dominant satellite-to-satellite and core-to-satellite coupling. High robustness against satellite disorder was proved by UV/vis diffuse reflectance (integrating sphere) measurements. Generalized multiparticle Mie theory (GMMT) simulations were employed to describe the electromagnetic coupling within the nanoclusters. The close correlation of structure and optical property allows for the rational design of core/satellite nanoclusters with tailored plasmonics and well-defined near-field enhancement, with perspectives for applications such as surface-enhanced spectroscopies.
Hydrolysis Stability of Bidentate Phosphites Utilized as Modifying Ligands in the Rh-Catalyzed n-Regioselective Hydroformylation of Olefins
2016, Zhang, Baoxin, Jiao, Haijun, Michalik, Dirk, Kloß, Svenja, Deter, Lisa Marie, Selent, Detlef, Spannenberg, Anke, Franke, Robert, Börner, Armin
The stability of ligands and catalysts is an almost neglected issue in homogeneous catalysis, but it is crucial for successful application of this methodology in technical scale. We have studied the effect of water on phosphites, which are the most applied cocatalysts in the n-regioselective homogeneous Rh-catalyzed hydroformylation of olefins. The stability of the bidentate nonsymmetrical diphosphite L1, as well as its two monophosphite constituents L2 and L3, toward hydrolysis was investigated by means of in situ NMR spectroscopy under similar conditions as applied in industry. Hydrolysis pathways, intermediates, and kinetics were clarified. DFT calculations were used to support the experimentally found data. The acylphosphite unit L2, which reacts with water in an unselective manner, was proven to be much less stable than the phenolphosphite L3. The stability of the bidentate ligand L1 can be therefore mainly attributed to its phenolphosphite moiety. With an excess of water, the hydrolysis of L1 and L2 as well as their Rh-complexes is first-order with respect to the phosphite. Surprisingly, coordination to Rh significantly stabilizes the monodentate ligand L2, while in strong contrast, the bidentate ligand L1 decomposes faster in the Rh complex. NMR spectroscopy provided evidence for the existence of species from decomposition of phosphites, which can likewise coordinate as ligands to the metal. Electron-withdrawing groups in the periphery of the acylphosphite moiety decrease the stability of L1, whereas 3,5-disubstituted salicylic acid derivatives with bulky groups showed superior stability. These modifications of L1 also give rise to different catalytic performances in the n-regioselective hydroformylation of n-octenes and 2-pentene, from which the 3,5-di-t-butyl-substituted ligand offered a higher n-regioselectivity accompanied by a lowering of the reaction rate in comparison to the parent ligand L1.
Conformations of a Long Polymer in a Melt of Shorter Chains: Generalizations of the Flory Theorem
2015, Lang, Michael, Rubinstein, Michael, Sommer, Jens-Uwe
Large-scale simulations of the swelling of a long N-mer in a melt of chemically identical P-mers are used to investigate a discrepancy between theory and experiments. Classical theory predicts an increase of probe chain size R ∼ P–0.18 with decreasing degree of polymerization P of melt chains in the range of 1 < P < N1/2. However, both experiment and simulation data are more consistent with an apparently slower swelling R ∼ P–0.1 over a wider range of melt degrees of polymerization. This anomaly is explained by taking into account the recently discovered long-range bond correlations in polymer melts and corrections to excluded volume. We generalize the Flory theorem and demonstrate that it is in excellent agreement with experiments and simulations.
Polypropylene/Layered Double Hydroxide Nanocomposites: Influence of LDH Intralayer Metal Constituents on the Properties of Polypropylene
2017, Nagendra, Baku, Rosely, C. V. Sijla, Leuteritz, Andreas, Reuter, Uta, Gowd, E. Bhoje
Sonication-assisted delamination of layered double hydroxides (LDHs) resulted in smaller-sized LDH nanoparticles (∼50-200 nm). Such delaminated Co-Al LDH, Zn-Al LDH, and Co-Zn-Al LDH solutions were used for the preparation of highly dispersed isotactic polypropylene (iPP) nanocomposites. Transmission electron microscopy and wide-angle X-ray diffraction results revealed that the LDH nanoparticles were well dispersed within the iPP matrix. The intention of this study is to understand the influence of the intralayer metal composition of LDH on the various properties of iPP/LDH nanocomposites. The sonicated LDH nanoparticles showed a significant increase in the crystallization rate of iPP; however, not much difference in the crystallization rate of iPP was observed in the presence of different types of LDH. The dynamic mechanical analysis results indicated that the storage modulus of iPP was increased significantly with the addition of LDH. The incorporation of different types of LDH showed no influence on the storage modulus of iPP. But considerable differences were observed in the flame retardancy and thermal stability of iPP with the type of LDH used for the preparation of nanocomposites. The thermal stability (50% weight loss temperature (T0.5)) of the iPP nanocomposite containing three-metal LDH (Co-Zn-Al LDH) is superior to that of the nanocomposites made of two-metal LDH (Co-Al LDH and Zn-Al LDH). Preliminary studies on the flame-retardant properties of iPP/LDH nanocomposites using microscale combustion calorimetry showed that the peak heat release rate was reduced by 39% in the iPP/Co-Zn-Al LDH nanocomposite containing 6 wt % LDH, which is higher than that of the two-metal LDH containing nanocomposites, iPP/Co-Al LDH (24%) and iPP/Zn-Al LDH (31%). These results demonstrated that the nanocomposites prepared using three-metal LDH showed better thermal and flame-retardant properties compared to the nanocomposites prepared using two-metal LDH. This difference might be due to the better char formation capability of three-metal LDH compared to that of two-metal LDH.
Iron-Based Binary Catalytic System for the Valorization of CO2 into Biobased Cyclic Carbonates
2016, Büttner, Hendrik, Grimmer, Christoph, Steinbauer, Johannes, Werner, Thomas
The atom economic conversion of epoxidized vegetable oils and fatty acid derivatives with CO2 into cyclic carbonates permits the synthesis of novel oleo compounds from renewable resources as well as the valorization of CO2 as a C1-building block. Organic phosphorus salts proved to be selective catalysts for this reaction. In a widespread screening 11 inexpensive and nontoxic iron salts were evaluated as cocatalysts to enhance the reaction rate. In the presence of 0.25 mol % iron chloride the selectivity and conversion were significantly improved. The reaction parameters were optimized under solvent-free conditions, and the scope and limitation were evaluated for 9 epoxidized fatty acid esters and 4 epoxidized vegetable oils. The biobased carbonates were isolated in excellent yields up to 95% and can be considered to be based on 100% CO2 in respect to carbon. This binary catalyst system features high efficiency and plain simplicity while valorizing CO2 into cyclic carbonates based on renewable feedstocks.