Self-Assembly ofmeso-Pyridylporphyrins and Zinc Phthalocyanines Through Axial Coordination

Author(s):  
Xi-you Li ◽  
Dennis K. P. Ng
2020 ◽  
Vol 20 (4) ◽  
pp. 6-26
Author(s):  
V. A. Burmistrov ◽  
V. V. Aleksandriiskii ◽  
I. V. Novikov ◽  
O. I. Koifman

Induction of helical mesophases by incorporating chiral dopants into the nematics matrix is the promising modern trends in the chemistry of liquid crystals. This process is associated with a unique phenomenon - an amplification of chirality in liquid-crystalline phases, which ensures the detection of enantiomers by their chiral induction, much more sensitive than other methods. The relevance of this approach is due to the need to create perspective electro-optical devices operating with ultra-low control voltages based on twist effects, chromatographic stationary phases with high chiral selectivity, flexible magnets, photo-sensitive nanostructures, and other smart LC materials. The successful solution of these problems is impossible without experimental research and theoretical comprehension of the mechanisms of third level chiral transfer optically active dopant – nematic liquid crystal. In the last decade, a large number of works have appeared on the solution of these problems. This review is devoted to a generalization of the experimental results and a theoretical description of the transfer of molecular chirality to orientationally ordered systems with the participation of both chiral molecular substituents with an asymmetric carbon atom and planar or quasi-planar fragments chirally distorted relative to each other. The stereochemical aspects of induction associated with the structural correspondences of the dopant and nematic liquid crystal, as well as the main classes of optically active additives, are discussed. Application of metal complexes, both Werner and macroheterocyclic, are presented. Special attention is paid to the results of the mechanisms study of chiral transfer due to various intermolecular interactions: hydrogen bonding, axial coordination, and the formation of inclusion compounds. The high efficiency of induction of spiral mesophases has been demonstrated with a combination of different self-assembly mechanisms in liquid crystal - chiral additive systems.


2009 ◽  
Vol 13 (02) ◽  
pp. 266-274 ◽  
Author(s):  
Francisco J. Céspedes-Guirao ◽  
Luis Martín-Gomis ◽  
Fernando Fernández-Lázaro ◽  
Ángela Sastre-Santos

The synthesis and characterization of two novel tetrasubstituted zinc phthalocyanines bearing bulky alkylaryloxy substituents in the so-called peripheral (1) and non-peripheral (2) positions is reported. Due to the presence of these bulky substituents, the non-peripheral substituted ZnPc 2 can be isolated as a pure regioisomer just by column chromatography. This is the first case where an α,α,α,α-tetrasubstituted regioisomer is isolated by column chromatography. Moreover, we describe the supramolecular complexation of both Pcs with the new pyridine-substituted trinitrofluorenone derivative TNFPy (3), whose synthesis and characterization is also commented. 1 H NMR titration experiments show that the system 2/3 presents a binding constant 35 times higher than system 1/3, which suggests a better accessibility to the metallic center.


2013 ◽  
Vol 575-576 ◽  
pp. 123-129
Author(s):  
Zhuang Dong Yuan ◽  
Jing Xia Wang ◽  
Ning Sheng

DABCO (1, 4-diazabicyclo [2.2.2] octane) has been used in combination with pentameric zinc porphyrin-pyrene array 1 to form well-defined supramolecular arrays through axial coordination. The self-assembly process has been investigated by a wide range of spectroscopic methods including UV-vis, fluorescence emission and 1H NMR techniques.


RSC Advances ◽  
2016 ◽  
Vol 6 (65) ◽  
pp. 60773-60779 ◽  
Author(s):  
Yu Wu ◽  
Jun-Xiang Zhang ◽  
Xiao-Xia Feng ◽  
Jia-Cheng Liu ◽  
Ren-Zhi Li ◽  
...  

Novel horizontal anchor zinc porphyrin assemblies via zinc-to-ligand axial coordination approach immobilized on TiO2 electrode surface have been impressive increased photoelectric conversion efficiency in supramolecular solar cell.


Author(s):  
D. Reis ◽  
B. Vian ◽  
J. C. Roland

Wall morphogenesis in higher plants is a problem still open to controversy. Until now the possibility of a transmembrane control and the involvement of microtubules were mostly envisaged. Self-assembly processes have been observed in the case of walls of Chlamydomonas and bacteria. Spontaneous gelling interactions between xanthan and galactomannan from Ceratonia have been analyzed very recently. The present work provides indications that some processes of spontaneous aggregation could occur in higher plants during the formation and expansion of cell wall.Observations were performed on hypocotyl of mung bean (Phaseolus aureus) for which growth characteristics and wall composition have been previously defined.In situ, the walls of actively growing cells (primary walls) show an ordered three-dimensional organization (fig. 1). The wall is typically polylamellate with multifibrillar layers alternately transverse and longitudinal. Between these layers intermediate strata exist in which the orientation of microfibrils progressively rotates. Thus a progressive change in the morphogenetic activity occurs.


Author(s):  
M. Kessel ◽  
R. MacColl

The major protein of the blue-green algae is the biliprotein, C-phycocyanin (Amax = 620 nm), which is presumed to exist in the cell in the form of distinct aggregates called phycobilisomes. The self-assembly of C-phycocyanin from monomer to hexamer has been extensively studied, but the proposed next step in the assembly of a phycobilisome, the formation of 19s subunits, is completely unknown. We have used electron microscopy and analytical ultracentrifugation in combination with a method for rapid and gentle extraction of phycocyanin to study its subunit structure and assembly.To establish the existence of phycobilisomes, cells of P. boryanum in the log phase of growth, growing at a light intensity of 200 foot candles, were fixed in 2% glutaraldehyde in 0.1M cacodylate buffer, pH 7.0, for 3 hours at 4°C. The cells were post-fixed in 1% OsO4 in the same buffer overnight. Material was stained for 1 hour in uranyl acetate (1%), dehydrated and embedded in araldite and examined in thin sections.


Author(s):  
Alan S. Rudolph ◽  
Ronald R. Price

We have employed cryoelectron microscopy to visualize events that occur during the freeze-drying of artificial membranes by employing real time video capture techniques. Artificial membranes or liposomes which are spherical structures within internal aqueous space are stabilized by water which provides the driving force for spontaneous self-assembly of these structures. Previous assays of damage to these structures which are induced by freeze drying reveal that the two principal deleterious events that occur are 1) fusion of liposomes and 2) leakage of contents trapped within the liposome [1]. In the past the only way to access these events was to examine the liposomes following the dehydration event. This technique allows the event to be monitored in real time as the liposomes destabilize and as water is sublimed at cryo temperatures in the vacuum of the microscope. The method by which liposomes are compromised by freeze-drying are largely unknown. This technique has shown that cryo-protectants such as glycerol and carbohydrates are able to maintain liposomal structure throughout the drying process.


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