Influence of the chain length and metal : ligand ratio on the self-organization processes of Cu2+ complexes of [1 + 1] 1H-pyrazole azamacrocycles

2020 ◽  
Vol 49 (25) ◽  
pp. 8614-8624 ◽  
Author(s):  
Alberto Lopera ◽  
Ariadna Gil-Martínez ◽  
Javier Pitarch-Jarque ◽  
Begoña Verdejo ◽  
Salvador Blasco ◽  
...  
Keyword(s):  
Chain Length ◽  
The Self ◽  
Self Organization ◽  
Ligand Ratio ◽  
Chain Lengths ◽  
Metal Ligand

The great versatility of the pyrazole moiety combined with polyamines of different chain lengths gives rise to remarkable coordination features.

Directive Effect of Chain Length in Modulating Peptide Nano-assemblies

2020 ◽  
Vol 27 (9) ◽  
pp. 923-929
Author(s):  
Gaurav Pandey ◽  
Prem Prakash Das ◽  
Vibin Ramakrishnan
Keyword(s):  
Electron Microscopy ◽  
Amino Acids ◽  
Light Scattering ◽  
Chain Length ◽  
Self Assembly ◽  
The Self ◽  
Ionic Charge ◽  
Self Assembling ◽  
Biophysical Techniques

Background: RADA-4 (Ac-RADARADARADARADA-NH2) is the most extensively studied and marketed self-assembling peptide, forming hydrogel, used to create defined threedimensional microenvironments for cell culture applications. Objectives: In this work, we use various biophysical techniques to investigate the length dependency of RADA aggregation and assembly. Methods: We synthesized a series of RADA-N peptides, N ranging from 1 to 4, resulting in four peptides having 4, 8, 12, and 16 amino acids in their sequence. Through a combination of various biophysical methods including thioflavin T fluorescence assay, static right angle light scattering assay, Dynamic Light Scattering (DLS), electron microscopy, CD, and IR spectroscopy, we have examined the role of chain-length on the self-assembly of RADA peptide. Results: Our observations show that the aggregation of ionic, charge-complementary RADA motifcontaining peptides is length-dependent, with N less than 3 are not forming spontaneous selfassemblies. Conclusion: The six biophysical experiments discussed in this paper validate the significance of chain-length on the epitaxial growth of RADA peptide self-assembly.

A Solvent-Dependent and Electrochemically Controlled Self-Assembling/Disassembling System

2003 ◽  
Vol 68 (9) ◽  
pp. 1647-1662 ◽  
Author(s):  
Valeria Amendola ◽  
Massimo Boiocchi ◽  
Yuri Diaz Fernandez ◽  
Carlo Mangano ◽  
Piersandro Pallavicini
Keyword(s):  
Equilibrium Mixture ◽  
Bidentate Ligand ◽  
Molecular Structures ◽  
The Self ◽  
Molar Ratio ◽  
Crystal And Molecular Structures ◽  
Self Assembling ◽  
Irreversible Oxidation ◽  
Irreversible Reduction ◽  
Metal Ligand

The bis-bidentate ligand R,S-1,2-diphenyl-N,N'-bis(2-quinolinemethylidene)ethane-1,2-diamine (ligand 4), containing two (iminomethyl)quinoline moieties separated by a cis-1,2-diphenylethylene spacer, forms stable complexes with both CuI and CuII. With CuII, the monomeric 1:1 complex [CuII(4)]2+ is obtained both in CH3CN and CH2Cl2. With CuI and overall 1:1 metal/ligand molar ratio, an equilibrium mixture is obtained in CH3CN, consisting of [CuI(4)2]+, [CuI2(4)2]2+ and [CuI2(4)(CH3CN)4]2+. The preponderant species is the two-metal one-ligand "open" complex [CuI2(4)(CH3CN)4]2+, in which each Cu+ cation is coordinated in a tetrahedral fashion by one (iminomethyl)quinoline unit and by two CH3CN molecules. Precipitation from the equilibrium mixture yields only crystals of [CuI2(4)(CH3CN)4](ClO4)2·2CH3CN, whose crystal and molecular structures have been determined. On the other hand, in the poorly coordinating CH2Cl2 solvent, only the dimeric helical [CuI2(4)2]2+ complex is obtained, when the overall metal/ligand 1:1 molar ratio is chosen. Addition of large quantities of acetonitrile to solutions of [CuI2(4)2]2+ in dichlorometane results in the formation of [CuI2(4)(CH3CN)4]2+, i.e. in the solvent-driven disassembling of the CuI helicate. While electrochemistry in CH3CN is poorly defined due to the presence of more than one CuI species, cyclic voltammetry experiments carried out in CH2Cl2 revealed a well defined behavior, with irreversible oxidation of [CuI2(4)2]2+ and irreversible reduction of [CuII(4)]2+ taking place at separate potentials (∆E ≈ 700 mV). Irreversibility and separation of the redox events are due to the self-assembling and disassembling processes following the reduction and oxidation, respectively.

scholarly journals Self-Assembled Nanomaterials Based on Complementary Sn(IV) and Zn(II)-Porphyrins, and Their Photocatalytic Degradation for Rhodamine B Dye

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3598
Author(s):  
Nirmal K. Shee ◽  
Hee-Joon Kim
Keyword(s):  
Aqueous Solution ◽  
Visible Light Irradiation ◽  
Rhodamine B ◽  
Self Assembly ◽  
The Self ◽  
Assembly Process ◽  
Absorption Bands ◽  
Ligand Coordination ◽  
Rhodamine B Dye ◽  
Metal Ligand

A series of porphyrin triads (1–6), based on the reaction of trans-dihydroxo-[5,15-bis(3-pyridyl)-10,20-bis(phenyl)porphyrinato]tin(IV) (SnP) with six different phenoxy Zn(II)-porphyrins (ZnLn), was synthesized. The cooperative metal–ligand coordination of 3-pyridyl nitrogens in the SnP with the phenoxy Zn(II)-porphyrins, followed by the self-assembly process, leads to the formation of nanostructures. The red-shifts and remarkable broadening of the absorption bands in the UV–vis spectra for the triads in CHCl3 indicate that nanoaggregates may be produced in the self-assembly process of these triads. The emission intensities of the triads were also significantly reduced due to the aggregation. Microscopic analyses of the nanostructures of the triads reveal differences due to the different substituents on the axial Zn(II)-porphyrin moieties. All these nanomaterials exhibited efficient photocatalytic performances in the degradation of rhodamine B (RhB) dye under visible light irradiation, and the degradation efficiencies of RhB in aqueous solution were observed to be 72~95% within 4 h. In addition, the efficiency of the catalyst was not impaired, showing excellent recyclability even after being applied for the degradation of RhB in up to five cycles.

scholarly journals Phenylalkylammonium passivation enables perovskite light emitting diodes with record high-radiance operational lifetime: the chain length matters

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yuwei Guo ◽  
Sofia Apergi ◽  
Nan Li ◽  
Mengyu Chen ◽  
Chunyang Yin ◽  
...  
Keyword(s):  
Chain Length ◽  
Quantum Efficiency ◽  
External Quantum Efficiency ◽  
Light Emitting Diodes ◽  
Surface Defects ◽  
Theoretical Modelling ◽  
Ion Migration ◽  
Light Emitting ◽  
Operational Lifetime ◽  
Chain Lengths

AbstractPerovskite light emitting diodes suffer from poor operational stability, exhibiting a rapid decay of external quantum efficiency within minutes to hours after turn-on. To address this issue, we explore surface treatment of perovskite films with phenylalkylammonium iodide molecules of varying alkyl chain lengths. Combining experimental characterization and theoretical modelling, we show that these molecules stabilize the perovskite through suppression of iodide ion migration. The stabilization effect is enhanced with increasing chain length due to the stronger binding of the molecules with the perovskite surface, as well as the increased steric hindrance to reconfiguration for accommodating ion migration. The passivation also reduces the surface defects, resulting in a high radiance and delayed roll-off of external quantum efficiency. Using the optimized passivation molecule, phenylpropylammonium iodide, we achieve devices with an efficiency of 17.5%, a radiance of 1282.8 W sr−1 m−2 and a record T50 half-lifetime of 130 h under 100 mA cm−2.

scholarly journals Influence of Salt on the Self-Organization in Solutions of Star-Shaped Poly-2-alkyl-2-oxazoline and Poly-2-alkyl-2-oxazine on Heating

Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1152
Author(s):  
Tatyana Kirila ◽  
Anna Smirnova ◽  
Alla Razina ◽  
Andrey Tenkovtsev ◽  
Alexander Filippov
Keyword(s):  
Phase Separation ◽  
Salt Concentration ◽  
Monomer Unit ◽  
Salt Content ◽  
The Self ◽  
Self Organization ◽  
Phase Separation Temperature ◽  
The Core ◽  
Separation Temperature ◽  
Water Salt

The water–salt solutions of star-shaped six-arm poly-2-alkyl-2-oxazines and poly-2-alkyl-2-oxazolines were studied by light scattering and turbidimetry. The core was hexaaza[26]orthoparacyclophane and the arms were poly-2-ethyl-2-oxazine, poly-2-isopropyl-2-oxazine, poly-2-ethyl-2-oxazoline, and poly-2-isopropyl-2-oxazoline. NaCl and N-methylpyridinium p-toluenesulfonate were used as salts. Their concentration varied from 0–0.154 M. On heating, a phase transition was observed in all studied solutions. It was found that the effect of salt on the thermosensitivity of the investigated stars depends on the structure of the salt and polymer and on the salt content in the solution. The phase separation temperature decreased with an increase in the hydrophobicity of the polymers, which is caused by both a growth of the side radical size and an elongation of the monomer unit. For NaCl solutions, the phase separation temperature monotonically decreased with growth of salt concentration. In solutions with methylpyridinium p-toluenesulfonate, the dependence of the phase separation temperature on the salt concentration was non-monotonic with minimum at salt concentration corresponding to one salt molecule per one arm of a polymer star. Poly-2-alkyl-2-oxazine and poly-2-alkyl-2-oxazoline stars with a hexaaza[26]orthoparacyclophane core are more sensitive to the presence of salt in solution than the similar stars with a calix[n]arene branching center.

scholarly journals Modification of Mechanical Properties of High-Strength Titanium Alloys VT23 and VT23M Due to Impact-Oscillatory Loading

Metals ◽  
2019 ◽  
Vol 9 (1) ◽  
pp. 80 ◽  
Author(s):  
Mykola Chausov ◽  
Janette Brezinová ◽  
Andrii Pylypenko ◽  
Pavlo Maruschak ◽  
Liudmyla Titova ◽  
...  
Keyword(s):  
Mechanical Properties ◽  
Titanium Alloys ◽  
High Strength ◽  
The Self ◽  
Self Organization ◽  
Two Phase ◽  
Rolled Metal ◽  
Technological Method ◽  
Equilibrium Processes ◽  
Production Conditions

A simple technological method is proposed and tested experimentally, which allows for the improvement of mechanical properties in sheet two-phase high-strength titanium alloys VT23 and VT23M on the finished product (rolled metal), due to impact-oscillatory loading. Under impact-oscillatory loading and dynamic non-equilibrium processes (DNP) are realized in titanium alloys, leading to the self-organization of the structure. As a result, the mechanical properties of titanium alloys vary significantly with subsequent loading after the realization of DNP. In this study, the test modes are found, which can be used in the production conditions.

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