Synthesis and mesogenic properties of several homologous series of aldose dialkyl dithioacetals. A model for their behaviour

Abstract

Ten homologous series (n-butyl through n-decyl) of aldose S,S-acetals (D-glucose, D-galactose, D-mannose, L-rhamnose, 2-deoxy-D-glucose, D-xylose, D-lyxose, D- or L-arabinose, D-ribose and 2-deoxy-D-ribose) have been prepared. Most of these compounds form thermotropic liquid crystals, the exceptions being the entire L-rhamnose series and some of the derivatives with the shortest alkyl chains. All of the compounds have been investigated with differential scanning calorimetry and polarization microscopy. Some temperature dependent powder X-ray data are also presented. A model is proposed which correlates the carbohydrate configuration with the melting behaviour. On the basis of now available behaviourial characteristics, visual inspection, mixing experiments and precedent, the mesophase is identified as smectic A_d, the partially overlapping carbohydrate moieties being in the centre and the aliphatic chains pointing outward at an angle of about 62°. Despite the intrinsic chirality of all the carbohydrate mesogens, no evidence for chiral mesophases was found, not even after introduction of a homochiral branched alkyl chain.     

Efficient Green‐Light‐Emitting Electrochemical Cells Based on Ionic Iridium Complexes with Sulfone‐Containing Cyclometalating Ligands

A new approach to obtain green‐emitting iridium(III) complexes is described. The synthetic approach consists of introducing a methylsulfone electron‐withdrawing substituent into a 4‐phenylpyrazole cyclometalating ligand in order to stabilize the highest‐occupied molecular orbital (HOMO). Six new complexes have been synthesized incorporating the conjugate base of 1‐(4‐(methylsulfonyl)phenyl)‐1 H‐pyrazole as the cyclometalating ligand. The complexes show green emission and very high photoluminescence quantum yields in both diluted and concentrated films. When used as the main active component in light‐emitting electrochemical cells (LECs), green electroluminance is observed. High efficiencies and luminances are obtained at low driving voltages. This approach for green emitters is an alternative to the widely used fluorine‐based substituents in the cyclometalating ligands and opens new design possibilities for the synthesis of green emitters for LECs.     

Giant spin splitting through surface alloying

The long-range ordered surface alloy Bi/Ag(111) is found to exhibit a giant spin splitting of its surface electronic structure due to spin-orbit coupling, as is determined by angle-resolved photoelectron spectroscopy. First-principles electronic structure calculations fully confirm the experimental findings. The effect is brought about by a strong in-plane gradient of the crystal potential in the surface layer, in interplay with the structural asymmetry due to the surface-potential barrier. As a result, the spin polarization of the surface states is considerably rotated out of the surface plane.     

Imaging the In Vivo Degradation of Tissue Engineering Implants by Use of Supramolecular Radiopaque Biomaterials

For in situ tissue engineering (TE) applications it is important that implant degradation proceeds in concord with neo‐tissue formation to avoid graft failure. It will therefore be valuable to have an imaging contrast agent (CA) available that can report on the degrading implant. For this purpose, a biodegradable radiopaque biomaterial is presented, modularly composed of a bisurea chain‐extended polycaprolactone (PCL2000‐U4U) elastomer and a novel iodinated bisurea‐modified CA additive (I‐U4U). Supramolecular hydrogen bonding interactions between the components ensure their intimate mixing. Porous implant TE‐grafts are prepared by simply electrospinning a solution containing PCL2000‐U4U and I‐U4U. Rats receive an aortic interposition graft, either composed of only PCL2000‐U4U (control) or of PCL2000‐U4U and I‐U4U (test). The grafts are explanted for analysis at three time points over a 1‐month period. Computed tomography imaging of the test group implants prior to explantation shows a decrease in iodide volume and density over time. Explant analysis also indicates scaffold degradation. (Immuno)histochemistry shows comparable cellular contents and a similar neo‐tissue formation process for test and control group, demonstrating that the CA does not have apparent adverse effects. A supramolecular approach to create solid radiopaque biomaterials can therefore be used to noninvasively monitor the biodegradation of synthetic implants.     

A stereodivergent approach to substituted 4-hydroxypiperidines

A stereodivergent route toward both diastereomeric forms of functionalized 4-hydroxypiperidines has been successfully developed. This route involves biocatalytic generation of the enantiopure starting materials followed by functionalization via N-acyliminium ion-mediated CC-bond formation.     

Intra-organizational Networks and Performance: A Review

Intra-organizational network research had its first heyday during the empirical revolution in social sciences before World War II when it discovered the informal group within the formal organization. These studies comment on the classic sociological idea of bureaucracy being the optimal organization. Later relational interest within organizational studies gave way to comparative studies on the quantifiable formal features of organizations. There has been a resurgence in intra-organizational networks studies recently as the conviction grows that they are critical to organizational and individual performance. Along with methodological improvements, the theoretical emphasis has shifted from networks as a constraining force to a conceptualization that sees them as providing opportunities and finally, as social capital. Because of this shift it has become necessary not only to explain the differences between networks but also their outcomes, that is, their performance. It also implies that internal and external networks should no longer be treated separately.Research on differences between intra-organizational networks centers on the influence of the formal organization, organizational demography, technology and environment. Studies on outcomes deal with diffusion and adaptation of innovation; the utilization of human capital; recruitment, absenteeism and turnover; work stress and job satisfaction; equity; power; information efficiency; collective decision making; mobilization for and outcomes of conflicts; social control; profit and survival of firms and individual performance.Of all the difficulties that are associated with intra-organizational network research, problems of access to organizations and incomparability of research findings seem to be the most serious. Nevertheless, future research should concentrate on mechanisms that make networks productive, while taking into account the difficulties of measuring performance within organizations, such as the performance paradox and the halo-effect.     

The smallest length of binary 7–dimensional linear codes with prescribed minimum distance

Let n(k,d) denote the smallest value of n for which a binary (n,k,d) code exists. Then n(k, d) was known for all d, when k ?6. All values of n(7, d) will now be presented.     

Salt crystallization as damage mechanism in porous building materials--a nuclear magnetic resonance study

Salts can damage building materials by chemical reactions or crystallization, which is a serious threat to cultural heritage. In order to develop better conservation techniques, more knowledge of the crystallization processes is needed. In a porous material, the size of a salt crystal is limited by the sizes of the pores. It has been predicted that as a consequence, the solubility of a salt increases with decreasing pore size. This increase seems to be related to an increase of the stress generated by a crystal on the pore wall. It has been suggested that the resulting stress could become high enough to induce failure. We have studied the crystallization of salts in porous materials with well-defined pore sizes. Samples were saturated at 40 degrees C with saturated Na2SO4 and Na2CO3 solutions. Next we have cooled the samples to 0 degrees C and waited for nucleation. After nucleation occurred, the solubility in the porous material was measured with nuclear magnetic resonance (NMR) as a function of the temperature. The measurements on Na2CO3 indeed show an increase in solubility with a decrease in pore size. For Na2SO4, we did not observe a pore size-dependent solubility. However, we have to remark that these results show a metastable crystal phase. The results can be used to calculate the actual pressure exerted by the crystals onto the pore wall.     

Weakly dispersive band near the fermi level of GaMnAs due to Mn interstitials

The nature of the weakly dispersive electronic band near the Fermi level observed in photoemission experiments on the diluted magnetic semiconductor GaMnAs is investigated theoretically. The combination of experimental features appears puzzling. We show that the formation of the band is closely related to the presence of the Mn interstitial impurities. The states forming the band have predominantly minority-spin Mn-3d character. The low experimental Mn-3d intensity is explained by the low content of the interstitial Mn impurities. The features of the band are robust with respect to the calculational technique [local density approximation (LDA), LDA + U].