Twisting and planarization in push-pull ethylenes

As determined by X-ray crystallography, Meldrum's acid derivatives 8–19 feature dihedral angles around the central CC double bonds between 3 and 83°. Hydrogen bonds between substituents RHN and the carbonyl groups favour near-planarity. Sterically demanding substituents favour large dihedral angles and zwitterionic structures as in formula 20. AM1 calculations of the structures are in excellent agreement with the experimental X-ray data, provided a dielectric field is incorporated (?= 40). This can be ascribed to the highly polar (zwitterionic) nature of the molecules. It is further predicted that all these molecules, including those that are stabilised in a planar form by intramolecular hydrogen bonds, undergo rapid rotation about the central CC bonds at room temperature. DFT calculations incorporating a dielectric field model (PCM) are in excellent agreement with the near-perpendicular arrangement of the alkene moiety in 19.

Helical Twisting of Electrospun Liquid Crystalline Cellulose Micro- and Nanofibers

Helically twisted fibers can be produced by electrospinning liquid-crystalline cellulose solutions. Fiber topographies are studied by atomic force microscopy, scanning electron microscopy (see figure) and polarized optical microscopy. The fibers have a nearly universal pitch-to-diameter ratio and comprise both right- and left-handed helices.

Bending, twisting, and breaking CuCN chains to produce framework materials: the reactions of CuCN with alkali-metal halides

The reactions of the low-temperature polymorph of copper(I) cyanide (LT-CuCN) with concentrated aqueous alkali-metal halide solutions have been investigated. At room temperature, KX (X = Br and I) and CsX (X = Cl, Br, and I) produce the addition products K[Cu-2(CN)(2)Br](H2O)-H-. (I), K-3[Cu-6(CN)(6)I-3](.)2H(2)O (II), Cs[Cu-3(CN)(3)Cl] (III), Cs[Cu-3(CN)(3)Br] (IV), and Cs-2[Cu-4(CN)(4)I-2](H2O)-H-. (V), with 3-D frameworks in which the -(CuCN)- chains present in CuCN persist. No reaction occurs, however, with NaX (X = Cl, Br, I) or KCl. The addition compounds, I-V, reconvert to CuCN when washed. Both low- and high-temperature polymorphs of CuCN (LT- and HT-CuCN) are produced, except in the case of Cs[Cu-3(CN)(3)Cl] (III), which converts only to LT-CuCN. Heating similar AX-CuCN reaction mixtures under hydrothermal conditions at 453 K for 1 day produces single crystals of I-V suitable for structure determination. Under these more forcing conditions, reactions also occur with NaX (X = Cl, Br, I) and KCl. NaBr and KCl cause some conversion of LT-CuCN into HT-CuCN, while NaCl and NaI, respectively, react to form the mixed-valence Cu(I)/Cu(II) compounds [Cu-II(OH2)(4)][Cu-4(I)(CN)(6)], a known phase, and [Cu-II(OH2)(4)][Cu-4(I)(CN)(4)I-2] (VI), a 3-D framework, which contains infinite -(CuCN)- chains. After 3 days of heating under hydrothermal conditions, the reaction between KI and CuCN produces [Cu-II(OH2)(4)][Cu-2(I)(CN)I-2](2) (VII), in which the CuCN chains are broken into single Cu-CN-Cu units, which in turn are linked into chains via iodine atoms and then into layers via long Cu-C and Cu-Cu interactions.

Dynamical twisting and the b ghost in the pure spinor formalism

After adding an RNS-like fermionic vector ψ m to the pure spinor formalism, the non-minimal b ghost takes a simple form similar to the pure spinor BRST operator. The N=2 superconformal field theory generated by the b ghost and the BRST current can be interpreted as a dynamical twisting of the RNS formalism where the choice of which spin 1/2 ψ m variables are twisted into spin 0 and spin 1 variables is determined by the pure spinor variables that parameterize the coset SO(10)/U(5). © 2013 SISSA, Trieste, Italy.

A coupled proton-transfer and twisting-motion fluorescence probe for lipid bilayers

A new and sensitive molecular probe, 2-(2′-hydroxyphenyl)imidazo[1,2-a]pyridine (HPIP), for monitoring structural changes in lipid bilayers is presented. Migration of HPIP from water into vesicles involves rupture of hydrogen (H) bonds with water and formation of an internal H bond once the probe is inside the vesicle. These structural changes of the dye allow the occurrence of a photoinduced intramolecular proton-transfer reaction and a subsequent twisting/rotational process upon electronic excitation of the probe. The resulting large Stokes-shifted fluorescence band depends on the twisting motion of the zwitterionic phototautomer and is characterized in vesicles of dimyristoyl-phosphatidylcholine and in dipalmitoyl-phosphatidylcholine at the temperature range of interest and in the presence of cholesterol. Because the fluorescence of aqueous HPIP does not interfere in the emission of the probe within the vesicles, HPIP proton-transfer/twisting motion fluorescence directly allows us to monitor and quantify structural changes within bilayers. The static and dynamic fluorescence parameters are sensitive enough to such changes to suggest this photostable dye as a potential molecular probe of the physical properties of lipid bilayers.

p53-induced DNA bending and twisting: p53 tetramer binds on the outer side of a DNA loop and increases DNA twisting

DNA binding activity of p53 is crucial for its tumor suppressor function. Our recent studies have shown that four molecules of the DNA binding domain of human p53 (p53DBD) bind the response elements with high cooperativity and bend the DNA. By using A-tract phasing experiments, we find significant differences between the bending and twisting of DNA by p53DBD and by full-length human wild-type (wt) p53. Our data show that four subunits of p53DBD bend the DNA by 32–36°, whereas wt p53 bends it by 51–57°. The directionality of bending is consistent with major groove bends at the two pentamer junctions in the consensus DNA response element. More sophisticated phasing analyses also demonstrate that p53DBD and wt p53 overtwist the DNA response element by ≈35° and ≈70°, respectively. These results are in accord with molecular modeling studies of the tetrameric complex. Within the constraints imposed by the protein subunits, the DNA can assume a range of conformations resulting from correlated changes in bend and twist angles such that the p53–DNA tetrameric complex is stabilized by DNA overtwisting and bending toward the major groove at the CATG tetramers. This bending is consistent with the inherent sequence-dependent anisotropy of the duplex. Overall, the four p53 moieties are placed laterally in a staggered array on the external side of the DNA loop and have numerous interprotein interactions that increase the stability and cooperativity of binding. The novel architecture of the p53 tetrameric complex has important functional implications including possible p53 interactions with chromatin.

GLOBALIZATION OF TWISTED PARTIAL ACTIONS

Let A be a unital ring which is a product of possibly infinitely many indecomposable rings. We establish a criteria for the existence of a globalization for a given twisted partial action of a group on A. If the globalization exists, it is unique up to a certain equivalence relation and, moreover, the crossed product corresponding to the twisted partial action is Morita equivalent to that corresponding to its globalization. For arbitrary unital rings the globalization problem is reduced to an extendibility property of the multipliers involved in the twisted partial action.

On Quasi-Hopf Superalgebras

In this work we investigate several important aspects of the structure theory of the recently introduced quasi-Hopf superalgebras (QHSAs), which play a fundamental role in knot theory and integrable systems. In particular we introduce the opposite structure and prove in detail (for the graded case) Drinfeld's result that the coproduct Delta ' =_ (S circle times S) (.) T (.) Delta (.) S-1 induced on a QHSA is obtained from the coproduct Delta by twisting. The corresponding "Drinfeld twist" F-D is explicitly constructed, as well as its inverse, and we investigate the complete QHSA associated with Delta '. We give a universal proof that the coassociator Phi ' = (S circle times S circle times S) Phi (321) and canonical elements alpha ' = S(beta), beta ' = S(alpha) correspond to twisting, the original coassociator Phi = Phi (123) and canonical elements alpha, beta with the Drinfeld twist F-D. Moreover in the quasi-tri angular case, it is shown algebraically that the R-matrix R ' = (S circle times S)R corresponds to twisting the original R-matrix R with F-D. This has important consequences in knot theory, which will be investigated elsewhere.

Transfer matrix eigenvalues of the anisotropic multiparametric U model

A multiparametric extension of the anisotropic U model is discussed which maintains integrability. The R-matrix solving the Yang-Baxter equation is obtained through a twisting construction applied to the underlying U-q(sl (2/1)) superalgebraic structure which introduces the additional free parameters that arise in the model. Three forms of Bethe ansatz solution for the transfer matrix eigenvalues are given which we show to be equivalent.

Dendrimer intercalation in layered double hydroxides

New organic/inorganic (O/I) hybrid assemblies based on Layered Double Hydroxide (LDH) with polyamide amine dendrimer (PAMAM, generation -0.5 and generation +0.5) were prepared by two different routes using either the direct coprecipitation at constant pH or the anion exchange procedure in double surfactant S(+)S(-) phases. The obtained materials were characterized by means of powder X-ray diffraction, thermal gravimetric analysis associated with mass spectrometry, and Fourier-transform infrared spectroscopy. X-ray powder diffraction pattern of the O/I LDH assembly exhibit characteristic profiles of LDH-based materials with basal spacing depending on the nature of the dendrimer. Indeed, for both synthetic procedures, interleaved PAMAM -0.5 gives rise to an interlayer space in agreement with a perpendicular molecular arrangement against the layer of the host structure. For PAMAM+0.5, considering its spherical dimension, a much smaller basal spacing was observed. This observation was interpreted as shrinkage of the molecule to accommodate the interlayer LDH gap, which was rendered possible by the bond angle twisting within PAMAM-0.5. FTIR spectra confirm the presence of both moieties inside both Zn(2)Al/PAMAM G-0.5 and Zn(2)Al/PAMAM G+0.5 assemblies. Finally, thermal analysis associated with mass spectrometry confirm this composition, and in situ temperature XRD data reveal that the highly constrained arrangement for the generation +0.5 is not accompanied by a gain in thermal structural stability; in fact, the assembly prepared from PAMAM -0.5 is more stable. Both O/I PAMAM LDH assemblies constitute well-defined materials which are candidate for catalytic applications.

2-Methoxy-6-methyl-3-nitro-4-(2-nitroprop-1-enyl)phenyl acetate

In the title compound, C13H14N2O7, steric crowding around the aromatic ring results in significant out-of-plane twisting of the nitro, methoxy, acetoxy and 2-nitropropenyl functional groups. These distortions are explained by comparison with less congested substituted benzene analogues.