Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties

The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role.     

Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals

We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by ¹H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases.     

煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

Self-Assembly of C3 Symmetric Rigid Macrolactams into Very Polar and Porous Trigonal Crystals

Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C₃-symmetric rings incorporating conjugated alkenes and dienes. All three C₃-symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively. All lactams stack on top of each other, through H-bonds and van der Waals noncovalent interactions, leading to endless supramolecular cylinders and tubes. The largest member of the family leads to tubes, the central pores of which is wide enough to let water in. A common feature of all the lactams is their very large dipole, of around 9 D, according to DFT calculations. Surprisingly, all the resulting cylinders and tubes pack side by side in the crystals, with all the dipoles pointing to the same direction. As a result, all three crystals are anisotropic and appear to be the first members of a new kind of highly polar crystals.     

Organic–Inorganic Hybrid Gold Halide Perovskites: Structural Diversity through Cation Size

Crystal structures of a series of organic–inorganic hybrid gold iodide perovskites, formulated as A₂[Au^II₂][Au^IIII₄] [A=methylammonium (MA) ( 1 ) and formamidinium (FA) ( 2 )], A′₂[I₃]_1−x[Au^II₂]_x[Au^IIII₄] [A′=imidazolium (IMD) ( 3 ), guanidinium (GUA) ( 4 ), dimethylammonium (DMA) ( 5 ), pyridinium (PY) ( 6 ), and piperizinium (PIP) ( 7 )], systematically changed depending on the cation size. In addition, triiodide (I₃⁻) ions were partly incorporated into the AuI₂⁻ sites of 3 – 7 , whereas they were not incorporated into those of 1 and 2 . Such a difference comes from the size of the organic cation. Optical absorption spectra showed characteristic intervalence charge-transfer bands from Au^I to Au^III species, and the optical band gap increased as the size of the cation became larger.     

Cover Picture: Arresting,Fixing, and Separating Dimers Composed of Uniform Silica Colloidal Spheres (Adv. Funct. Mater. 12/2006)

In colloidal suspensions of silica, particles undergo constant collisions. By controlling various parameters, the repulsive barrier can be reduced, thereby substantially increasing the number of collision‐induced dimerization events. Xia and co‐workers report on p. 1627 that the dimers could be arrested and then permanently fixed by introducing a small amount of fresh tetraethylorthosilicate into the colloidal suspension, with monodisperse dimer yields of up to 50 %. This yield could be increased to 80 % by centrifugation in a density gradient medium. When fresh tetraethylorthosilicate is introduced into a colloidal suspension of silica spheres, it hydrolyzes and condenses in situ to arrest and fix the dimers resulting from constant collisions between the spheres. By optimizing the experimental parameters (including the length of aging time) and the diameter of the silica spheres, as well as the concentrations of counterions, water, and ammonia, it is possible to routinely produce monodisperse dimers with a yield as high as 50 %. When combined with centrifugation using a density gradient medium, the yield of such dimers could be further increased to 80 %. It is believed that this method will provide a simple and versatile approach to the high‐volume production of dimers from spherical colloids composed of different materials. These dimers may find widespread use in a range of applications such as fabrication of photonic crystals and fundamental studies related to colloidal science.     

Panchromatic Chromophore Mixtures in an AlPO4‐5 Molecular Sieve: Spatial Separation Effects and Energy Transfer Cascades

Dye‐loaded AlPO₄‐5 single crystals were prepared by microwave‐assisted hydrothermal synthesis from a batch, containing a mixture of three chromophores (Coumarin 40, Rhodamine BE50, and Oxazine 1) differing in their absorption range, molecular dimensions, and solubilities. Confocal fluorescence images reveal a spatial separation effect of the dye molecules, where the slimmer, more‐soluble dye molecule (Coumarin 40) is uniformly distributed in the body of the single crystal, and the bulky and/or less‐soluble ones (Rhodamine BE50, Oxazine 1) are situated in distinct domains. Visible spectra show good panchromatic absorption of visible light. Fluorescence lifetime measurements indicate the presence of an energy transfer cascade of the entirely fixed dye molecules from Coumarin 40 to Oxazine 1. The transfer mechanism is predominantly radiative.     

Mixed Mode VLSI Implementation of a Neural Associative Memory

A mixed mode digital/analog special purpose VLSI hardware implementation of an associative memory with neural architecture is presented. The memory concept is based on a matrix architecture with binary storage elements holding the connection weights. To enhance the processing speed analog circuit techniques are applied to implement the algorithm for the association. To keep the memory density as high as possible two design strategies are considered. First, the number of transistors per storage element is kept to a minimum. In this paper a circuit technique that uses a single 6-transistor cell for weight storage and analog signal processing is proposed. Second, the device precision has been chosen to a moderate level to save area as much as possible. Since device mismatch limits the performance of analog circuits, the impact of device precision on the circuit performance is explicitly discussed. It is shown that the device precision limits the number of rows activated in parallel. Since the input vector as well as the output vector are considered to be sparsely coded it is concluded, that even for large matrices the proposed circuit technique is appropriate and ultra large scale integration with a large number of connection weights is feasible.     

Cycle and circle tests of balance in gain graphs: Forbidden minors and their groups

We examine two criteria for balance of a gain graph, one based on binary cycles and one on circles. The graphs for which each criterion is valid depend on the set of allowed gain groups. The binary cycle test is invalid, except for forests, if any possible gain group has an element of odd order. Assuming all groups are allowed, or all abelian groups, or merely the cyclic group of order 3, we characterize, both constructively and by forbidden minors, the graphs for which the circle test is valid. It turns out that these three classes of groups have the same set of forbidden minors. The exact reason for the importance of the ternary cyclic group is not clear. © 2005 Wiley Periodicals, Inc. J Graph Theory     

Nonsensitiveness Regions for Threshold Ellipsoids

The problem is to determine nonsensitiveness regions for threshold ellipsoids within a regular mixed linear model.