scholarly journals Insight into the self-assembly of water-soluble perylene bisimide derivatives through a combined computational and experimental approach

Nanoscale ◽  
2019 ◽  
Vol 11 (34) ◽  
pp. 15917-15928 ◽  
Author(s):  
Emily R. Draper ◽  
Liam Wilbraham ◽  
Dave J. Adams ◽  
Matthew Wallace ◽  
Ralf Schweins ◽  
...  

We use a combination of computational and experimental techniques to study the self-assembly and gelation of amino-acid functionalised water-soluble perylene bisimides.


2019 ◽  
Author(s):  
Emily R. Draper ◽  
Liam Wilbraham ◽  
Dave J. Adams ◽  
Matthew Wallace ◽  
Martijn Zwijnenburg

We use a combination of computational and experimental techniques to study the self-assembly and gelation of water-soluble perylene bisimides derivatised at the imide position with an amino acid. Specifically, we study the likely structure of self-assembled aggregates of the alanine-functionalised perylene bisimide (PBI-A) and the thermodynamics of their formation using density functional theory and predict the UV-vis spectra of such aggregates using time-dependent density functional theory. We compare these predictions to experiments in which we study the evolution of the UV-Vis and NMR spectra and rheology of alkaline PBI-A solutions when gradually decreasing the pH. Based on the combined computational and experimental results, we show that PBI-A self-assembles at all pH values but that aggregates grow in size upon protonation. Gelation is driven not by aggregate growth but reduction of the aggregation surface-charge and a decrease in the colloidal stability of the aggregation with respect to agglomeration.



2019 ◽  
Author(s):  
Emily R. Draper ◽  
Liam Wilbraham ◽  
Dave J. Adams ◽  
Matthew Wallace ◽  
Martijn Zwijnenburg

We use a combination of computational and experimental techniques to study the self-assembly and gelation of water-soluble perylene bisimides derivatised at the imide position with an amino acid. Specifically, we study the likely structure of self-assembled aggregates of the alanine-functionalised perylene bisimide (PBI-A) and the thermodynamics of their formation using density functional theory and predict the UV-vis spectra of such aggregates using time-dependent density functional theory. We compare these predictions to experiments in which we study the evolution of the UV-Vis and NMR spectra and rheology of alkaline PBI-A solutions when gradually decreasing the pH. Based on the combined computational and experimental results, we show that PBI-A self-assembles at all pH values but that aggregates grow in size upon protonation. Gelation is driven not by aggregate growth but reduction of the aggregation surface-charge and a decrease in the colloidal stability of the aggregation with respect to agglomeration.



2019 ◽  
Author(s):  
Emily R. Draper ◽  
Liam Wilbraham ◽  
Dave J. Adams ◽  
Matthew Wallace ◽  
Martijn Zwijnenburg

We use a combination of computational and experimental techniques to study the self-assembly and gelation of water-soluble perylene bisimides derivatised at the imide position with an amino acid. Specifically, we study the likely structure of self-assembled aggregates of the alanine-functionalised perylene bisimide (PBI-A) and the thermodynamics of their formation using density functional theory and predict the UV-vis spectra of such aggregates using time-dependent density functional theory. We compare these predictions to experiments in which we study the evolution of the UV-Vis and NMR spectra and rheology of alkaline PBI-A solutions when gradually decreasing the pH. Based on the combined computational and experimental results, we show that PBI-A self-assembles at all pH values but that aggregates grow in size upon protonation. Gelation is driven not by aggregate growth but reduction of the aggregation surface-charge and a decrease in the colloidal stability of the aggregation with respect to agglomeration.



2017 ◽  
Vol 5 (16) ◽  
pp. 7555-7563 ◽  
Author(s):  
Michael C. Nolan ◽  
James J. Walsh ◽  
Laura L. E. Mears ◽  
Emily R. Draper ◽  
Matthew Wallace ◽  
...  

We show the importance of the self-assembly of a perylene bisimide on its photocatalytic activity.



Soft Matter ◽  
2020 ◽  
Vol 16 (22) ◽  
pp. 5250-5260 ◽  
Author(s):  
Sima Rezvantalab ◽  
Mostafa Keshavarz Moraveji ◽  
Mohammad Khedri ◽  
Reza Maleki

Nanoparticles (NPs) used for targeted delivery purposes are rapidly gaining importance in diagnostic and therapeutic fields.



2021 ◽  
Author(s):  
Jacquelyn Grace G Egan ◽  
Glen Brodie ◽  
Daniel McDowall ◽  
Andrew J Smith ◽  
Charlotte J. C. Edwards-Gayle ◽  
...  

Here in we investigate how apparent slight changes to the chemical structure of amino acid-functionalized perylene bisimides (PBIs) affect the self-assembled aggregates formed and their resulting physical and optical properties....



Soft Matter ◽  
2020 ◽  
Vol 16 (28) ◽  
pp. 6599-6607 ◽  
Author(s):  
Pijush Singh ◽  
Souvik Misra ◽  
Nayim Sepay ◽  
Sanjoy Mondal ◽  
Debes Ray ◽  
...  

The self-assembly and photophysical properties of 4-nitrophenylalanine (4NP) are changed with the alteration of solvent and final self-assembly state of 4NP in competitive solvent mixture and are dictated by the solvent ratio.



2004 ◽  
Vol 2004 (1) ◽  
pp. 51-62 ◽  
Author(s):  
Mourad Elhabiri ◽  
Josef Hamacek ◽  
Jean-Claude G. Bünzli ◽  
Anne-Marie Albrecht-Gary


2021 ◽  
Vol 22 (17) ◽  
pp. 9634
Author(s):  
Moran Aviv ◽  
Dana Cohen-Gerassi ◽  
Asuka A. Orr ◽  
Rajkumar Misra ◽  
Zohar A. Arnon ◽  
...  

Supramolecular hydrogels formed by the self-assembly of amino-acid based gelators are receiving increasing attention from the fields of biomedicine and material science. Self-assembled systems exhibit well-ordered functional architectures and unique physicochemical properties. However, the control over the kinetics and mechanical properties of the end-products remains puzzling. A minimal alteration of the chemical environment could cause a significant impact. In this context, we report the effects of modifying the position of a single atom on the properties and kinetics of the self-assembly process. A combination of experimental and computational methods, used to investigate double-fluorinated Fmoc-Phe derivatives, Fmoc-3,4F-Phe and Fmoc-3,5F-Phe, reveals the unique effects of modifying the position of a single fluorine on the self-assembly process, and the physical properties of the product. The presence of significant physical and morphological differences between the two derivatives was verified by molecular-dynamics simulations. Analysis of the spontaneous phase-transition of both building blocks, as well as crystal X-ray diffraction to determine the molecular structure of Fmoc-3,4F-Phe, are in good agreement with known changes in the Phe fluorination pattern and highlight the effect of a single atom position on the self-assembly process. These findings prove that fluorination is an effective strategy to influence supramolecular organization on the nanoscale. Moreover, we believe that a deep understanding of the self-assembly process may provide fundamental insights that will facilitate the development of optimal amino-acid-based low-molecular-weight hydrogelators for a wide range of applications.



2021 ◽  
Author(s):  
Bharti Koshti ◽  
Ramesh Singh ◽  
Vivekshinh Kshtriya ◽  
Shanka Walia ◽  
Dhiraj Bhatia ◽  
...  

<p>.<br></p><p>The self-assembly of single amino acids is very important topic of research since there are plethora of diseases like phenylketonuria, tyrosinemia, hypertryptophanemia, hyperglycinemia, cystinuria and maple syrup urine disease to name a few which are caused by the accumulation or excess of amino acids. These are in-born errors of metabolisms (IEM’s) which are caused due to the deficiency of enzymes involved in catabolic pathways of these enzymes. Hence, it is very pertinent to understand the fate of these excess amino acids in the body and their self-assembling behaviour at molecular level. From the previous literature reports it may be surmised that the single amino acids like Phenylalanine, Tyrosine, Tryptophan, Cysteine and Methionine assemble to amyloid like structures, and hence have important implications in the pathophysiology of IEM’s like phenylketonuria, tyrosinemia, hypertryptophanemia, cystinuria and hypermethioninemia respectively. In this manuscript we report the self-assembly of lysine hydrocholride to fiber like structures in deionized water. It could be observed that lysine assemble to globular structures in fresh condition and then gradually changes to fiber like morphologies by self-association over time after 24 hours. These fibers gradually change to tubular morphologies after 3 day followed by fractal irregular morphologies in 10 and 15 days respectively. Notably, lysine exists as positively charged amino acid at physiological pH and the amine groups in lysine remain protonated. Hence, the self-assembling properties of lysine hydrochloride in deionized water is also pertinent and give insights into the fate of this amino acid in body in case it remains unmetabolized. Further, MTT assays were done to analyse the toxicities of these aggregates and the assay suggest their cytotoxic nature on SHSY5Y neural cell lines. Hence, the aggregation of lysine may be attributed to the pathological symptoms caused in diseases like hyperlysinemia which is associated with the neurological problems like seizures and short-term memory as observed in case of amyloid diseases like Parkinson’s and Alzheimer’s to name a few.</p>



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