Effect of Tricarboxylic Acids on the Formation of Hydrogels with Melem or Melamine: Morphological, Structural and Rheological Investigations

Herein, aggregation behaviors of melem or melamine in the presence of three symmetric carboxylic acids (1,3,5-tris(4-carboxyphenyl)benzene (TPCA), 1,3,5-benzene-tri-carboxylic acid (BTA) and 1,3,5-cyclohexane-tri-carboxylic acid (CHTA)) have been performed to check the influence of acid on the formation of aggregated structures which have been investigated by optical microscopy, FESEM, FTIR, XRD and viscoelastic properties have been explored with rheological studies. Interestingly, melem, that has limited solubility in aqueous medium, forms aggregation that leads to the formation of hydrogels with TPCA. More significantly, hydrogel is formed here by matching the size selectivity. Melem forms hydrogel with only large tricarboxylic acid, whereas melamine produces hydrogel with any kind of its counterpart from small to large tricarboxylic acid derivatives. Present investigations and results provide the strategy of design of organic self-assembled materials having two component systems.

A chemosensor-based chiral coassembly with switchable circularly polarized luminescence

Fluorescent chemosensors represent fast response to analytes with pronounced luminescent variations. They are promising as potential candidates in controlling luminescence and chiroptical activities of self-assembled chiral systems, which however have not been accomplished to date. We present a coassembled multiple component system that could respond to SO2 derivatives, giving rise to dynamic aggregation behaviors and switchable luminescence as well as circularly polarized luminescence (CPL). Cholesteryl-naphthalimide and coumarin derivatives coassemble into vesicles and nanohelices under the solvent strategy, behaving as energy transfer donor and accepter respectively. Energy transfer enables CPL transition from green to red depending on the molar fraction. After the addition of SO2 derivatives, hypochromic shifts occur to CPL due to the nucleophilic addition reaction to coumarin domain, hindering energy transfer and allow for the emergence of pristine luminescence. Here, we show a protocol to control over luminescence and chiroptical features of supramolecular chiral self-assemblies using fluorescent chemosensors.

Influence of pH and ionic strength on the aggregation behaviors of xylan rich hemicelluloses with alkaline lignins

The evolution of xylan-rich hemicelluloses (XH) aggregation behaviors in the presence of alkaline lignins (AL) under a wide range of pH values and NaCl concentration were investigated via dynamic light scattering and turbidity measurements. XH isolated from wheat straw contain a xylose backbone with arabinose side chains and a small amount of phenol groups. XH tend to aggregate in solution due to their low ratio of arabinose to xylose and hydrophobic phenol groups. AL interact with XH through the phenol groups bonded to the hemicellulose main chain to form an AL-XH complex. As the pH value decreases, the particle size and turbidity of AL, XH and their bonded complex all increase. The size of the AL-XH complex agglomerate is greater than the size of a XH at the same pH value, which indicates that the self-assembly of lignin molecules initiate the aggregation of XH. The particle size and turbidity of XH and AL-XH complexes increase as the XH concentration increase. At low pH values, e.g., 6.0, the particle size of the AL-XH complex more obviously increases compared to the XH particles. The size and turbidity of the AL, XH, and AL-XH complex agglomerates increased as the NaCl concentration increased.

Evaluating Effect of Metallic Ions on Aggregation Behavior of Amyloid Aβ42 by AFM Imaging and SERS

In this study, self-assembled monolayer (SAM) method was employed to fabricate monolayer of β-amyloid peptides Aβ42 on gold substrate with a bolaamphiphile named thiol (MHA). Firstly, the samples of gold substrate (blank control), the MHA-modified substrate and the Aβ42-modified substrate were detected by X-ray photoelectron spectroscopy (XPS) to track the self-assembly process. The spectra of binding energy measured from these three sample surfaces could be well fitted with the corresponding monolayer’s composition, which means Aβ42 monolayer is well formed. Aggregation behaviors of Aβ42 in the absence and presence of metallic ions (Zn2+、Ca2+、Al3+) were then monitored by atomic force microscopy (AFM) and surface-enhanced Raman Scattering (SERS), respectively. The recorded surface morphology of different experimental groups obtained by AFM showed markedly different nanostructures, indicating occurrence of aggregation behaviors of Aβ42. In solutions with added metal ions, the increased size of surface structures was observed, which suggest the presence of metal cations promotes aggregation behavior between Aβ42 molecules. Furtherly, the interaction between Aβ42 and metal cations was investigated by SERS. The results demonstrate that the Raman strength of Aβ42 changes after the metal cation treatment. Taken together, the combined AFM imaging and Raman analyses show that the three kinds of metallic ions promote the process of Aβ42 aggregation.

Sulfation modification of dopamine in brain regulates aggregative behavior of animals

Behavioral plasticity and the underlying neuronal plasticity represent a fundamental capacity of animals to cope with environmental stimuli. Behavioral plasticity is controlled by complex molecular networks that act under different layers of regulation. While various molecules have been found to be involved in the regulation of plastic behaviors across species, less is known about how organisms orchestrate the activity of these molecules as part of a coherent behavioral response to varying environments. Here we discover a mechanism for the regulation of animal behavioral plasticity involving molecular sulfation in brain, a modification of substrate molecules by sulfotransferase (ST)-catalyzed addition of a sulfonate group (SO3) from an obligate donor, 3’-phosphoadenosine 5’-phosphosulfate (PAPS) to the substrates. We investigated aggregation behaviors of the migratory locusts, which are well-known for extreme phase change plasticity triggered by population density. The processes of PAPS biosynthesis acted efficiently on induction of locust behavioral transition: Inhibition of PAPS synthesis solicited a behavioral shift from gregarious to solitarious states; external PAPS dosage, by contrast, promoted aggregation in solitarious locusts. Genetic or pharmacological intervention in the sulfation catalyzation resulted into pronounced solitarizing effects. Analysis of substrate-specific STs suggests a widespread involvement of sulfated neurotransmitters in the behavioral response. Dopamine in brain was finally identified to be actively sulfate conjugated, and the sulfate conjugation enhanced the free DA-mediated behavioral aggregation. Similar results in Caenorhabditis elegans and mouse indicate that sulfation may be involved more broadly in the modulation of animal aggregation. These findings revealed a general mechanism that effectively regulates animal social-like behavioral plasticity possibly through sulfation-mediated modification of neural networks.

The metal cofactor zinc and interacting membranes modulate SOD1 conformation-aggregation landscape in an in vitro ALS Model

Aggregation of Cu-Zn superoxide dismutase (SOD1) is implicated in the motor neuron disease, ALS. Although more than 140 disease mutations of SOD1 are available, their stability or aggregation behaviors in membrane environment are not correlated with disease pathophysiology. Here, we use multiple mutational variants of SOD1 to show that the absence of Zn, and not Cu, significantly impacts membrane attachment of SOD1 through two loop regions facilitating aggregation driven by lipid induced conformational changes. These loop regions influence both the primary (through Cu intake) and the gain of function (through aggregation) of SOD1 presumably through a shared conformational landscape. Combining experimental and theoretical frameworks using representative ALS disease mutants, we develop a 'co-factor derived membrane association model' wherein mutational stress closer to the Zn (but not to the Cu) pocket is responsible for membrane association mediated toxic aggregation and survival time scale after ALS diagnosis.