Asymmetry in liquid crystalline hexaalkoxytriphenylene discotics

The synthesis and phase behaviour of a new series of unsymmetrically substituted hexaalkoxytriphenylene‐based liquid crystals are reported. One of the hexyloxy chains in hexahexyloxytriphenylene (HAT6) is replaced by either a shorter or a longer chain, HAT‐(OC₆H₁₃)₅(OC _n H_2n+1). Compounds with chain lengths n of 2–14, 16 and 18 were prepared and investigated. Compounds with n?13 were not liquid crystalline. For all compounds with n?12 Col_h textures were observed by polarizing microscopy. X‐ray investigations showed that the intercolumnar distance gradually increased with n from n = 2 to n = 12, while the interdisk distance (3.6 Å) remained constant. A small odd–even effect on the increase of the intercolumn distance with n was observed. This effect was also found in the change of ΔH of isotropization with n.     

Bis‐clickable Mesoporous Silica Nanoparticles: Straightforward Preparation of Light‐Actuated Nanomachines for Controlled Drug Delivery with Active Targeting

Bis(clickable) mesoporous silica nanospheres (ca. 100 nm) were obtained by the co‐condensation of TEOS with variable amounts (2–5 % each) of two clickable organosilanes in the presence of CTAB. Such nanoparticles could be easily functionalized with two independent functions using the copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) reaction to transform them into nanomachines bearing cancer cell targeting ligands with the ability to deliver drugs on‐demand. The active targeting was made possible after anchoring folic acid by CuAAC click reaction, whereas the controlled delivery was performed by clicked azobenzene fragments. Indeed, the azobenzene groups are able to obstruct the pores of the nanoparticles in the dark whereas upon irradiation in the UV or in the blue range, their trans‐to‐cis photoisomerization provokes disorder in the pores, enabling the delivery of the cargo molecules. The on‐command delivery was proven in solution by dye release experiments, and in vitro by doxorubicin delivery. The added value of the folic acid ligand was clearly evidenced by the difference of cell killing induced by doxorubicin‐loaded nanoparticles under blue irradiation, depending on whether the particles featured the clicked folic acid ligand or not.     

Improving charge transport in poly(3‐hexylthiophene) transistors via blending with an alkyl‐substituted phenylene–thiophene–thiophene–phenylene molecule

A prototypical semiconducting bicomponent system consisting of a conjugated polymer, that is, poly(3‐hexylthiophene) (P3HT), blended with a small thiophene containing conjugated molecule, that is, an alkyl‐substituted bisphenyl‐bithiophene [phenylene–thiophene–thiophene–phenylene (PTTP)], has been used as an electroactive active layer in field‐effect transistors (FETs). The self‐assembly of this bicomponent system at surfaces has been studied at different length scales, from the nanoscale to the macroscale, and compared with the behavior of monocomponent films of PTTP and P3HT. The correlation between morphology and electric properties of the semiconducting material is explored by fabricating prototypes of FETs varying the relative concentrations of the two‐component blend. The maximum charge carrier mobility value, achieved with a few percent of PTTP component, is not simply due to a uniform dispersion of the molecules in the polymer matrix, but rather to the generation of very long percolation paths, whose composition and electrical properties can be tuned with the PTTP concentration. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Algorithmic boundedness-from-below conditions for generic scalar potentials

Checking that a scalar potential is bounded from below (BFB) is an ubiquitous and notoriously difficult task in many models with extended scalar sectors. Exact analytic BFB conditions are known only in simple cases. In this work, we present a novel approach to algorithmically establish the BFB conditions for any polynomial scalar potential. The method relies on elements of multivariate algebra, in particular, on resultants and on the spectral theory of tensors, which is being developed by the mathematical community. We give first a pedagogical introduction to this approach, illustrate it with elementary examples, and then present the working Mathematica implementation publicly available at GitHub. Due to the rapidly increasing complexity of the problem, we have not yet produced ready-to-use analytical BFB conditions for new multi-scalar cases. But we are confident that the present implementation can be dramatically improved and may eventually lead to such results.     

Hypernuclear physics at \overline{\mbox{P}} anda

Samples obtained as a result of the valleriite synthesis process under different conditions (temperature and proportion Cu:Fe:Mg in the initial mixture) were investigated by ⁵⁷Fe M?ssbauer spectroscopy with attraction data of X-ray diffraction. Parameters of hyperfine interactions for valleriite were determined and crystal chemical identification of ⁵⁷Fe subspectra was carried out. It was found that valleriite was formed in samples synthesized at 150°C and 180°C and not formed in samples synthesized at 250°C.     

Intermolecular Domino Reaction of Two Aryl Iodides Involving Two CH Functionalizations

A palladium‐catalyzed intermolecular cross‐coupling of two aryl iodides is reported, giving polycyclic ring systems with a high level of convergence and efficiency.     

Hyperpolarization of Amino Acids in Water Utilizing Parahydrogen on a Rhodium Nanocatalyst

NMR offers many possibilities in chemical analysis, structural investigations, and medical diagnostics. Although it is broadly used, one of NMR spectroscopies main drawbacks is low sensitivity. Hyperpolarization techniques enhance NMR signals by more than four orders of magnitude allowing the design of new contrast agents. Parahydrogen induced polarization that utilizes the para-hydrogen's singlet state to create enhanced signals is of particular interest since it allows to produce molecular imaging agents within seconds. Herein, we present a strategy for signal enhancement of the carbonyl ¹³C in amino acids by using parahydrogen, as demonstrated for glycine and alanine. Importantly, the hyperpolarization step is carried out in water and chemically unmodified canonical amino acids are obtained. Our approach thus offers a high degree of biocompatibility, which is crucial for further application. The rapid sample hyperpolarization (within seconds) may enable the continuous production of biologically useful probes, such as metabolic contrast agents or probes for structural biology.