Self-assembled Aggregates Research Articles

Supramolecular biosolvent extraction of antioxidants from orange peel residues from the tea industry

The growing interest in natural antioxidants across various industries has spurred the development and use of alternative green methods for valorizing plant biomass. Supramolecular solvents (bioSUPRAS), composed of self-assembled amphiphilic aggregates, have shown significant potential for the recovery of high-value compounds from plant biomass for industrial applications while adhering to numerous green chemistry principles. In this study, we evaluated various bioSUPRAS (sponge bioSUPRAS of 1,2-octanediol and cubosomic bioSUPRAS of 1,2-hexanediol) and different extraction conditions for the recovery of antioxidants from orange peel waste generated by the tea industry. Sponge bioSUPRAS were selected as optimal and the best conditions for formation consisted of a medium of 15 % v/v of 1,3-propanediol as co-solvent and 85 % v/v of water (acidified with 1 % v/v acetic acid). The most suitable extraction conditions were 1:12 mL:g bioSUPRAS-to-solid ratio at room temperature for 30 min, resulting in a maximum yield of 12.9 ± 1.4 mg GAE/g. Using liquid chromatography coupled with high-resolution tandem mass spectrometry (LC-QTOF), we screened and quantified the natural compounds of interest, identifying the flavonoid hesperidin as the dominant antioxidant at 2.6 ± 0.06 mg/g. This research presents a promising method for valorizing underutilized orange peel waste and highlights the potential of these extracts as ingredients in new value-added formulations.

Graphene electrochemical biosensors combining effervescent solid-phase extraction (ESPE) for rapid, ultrasensitive, and simultaneous determination of DA, AA, and UA

Simultaneous monitoring of key metabolites like dopamine, ascorbic acid, and uric acid is essential for early disease diagnosis and evaluating treatment. Electrochemical techniques are increasingly used for precise, point-of-care testing (POCT) of these metabolites. Herein, a sample pretreatment method called effervescent solid-phase extraction (ESPE) was proposed for efficient enrichment of trace analytes for electrochemical detection. In an ESPE process, effervescent tablets made of gold nanoparticle-decorated graphene oxide (Au/GO) were first self-dispersed in a test solution to promote the enrichment of analytes on the Au/GO adsorbents, followed by the addition of flocculant effervescent tablets to cause Au/GO sheets to form self-assembled aggregates, which then can be efficiently collected by the foam electrodes. The entire sample pretreatment process operates without external power and takes only 5 min. With the assistance of the ESPE method, our electrochemical sensors achieve an ultralow detection limit for dopamine, ascorbic acid, and uric acid of 80 pM, 1.8 nM, and 460 pM, respectively, which are two to three orders of magnitude lower than the results obtained by the drop casting technique. The enhancement mechanism of our approach is based on increasing the contact probability with analytes through dynamic dispersion of the Au/GO adsorbents, in contrast to the static diffusion mechanism relied on Brownian motion. We also show that combining the ESPE solution kit with a portable micro-electrochemical workstation can attain the same detection level as HPLC in real urine samples. The proposed ESPE approach holds great promise for POCT applications in 2D material-based biosensors.

Synthesis of Polyether Block Copolymers from 1,2-Epoxybutane and AEOn and Comparative Study of Physicochemical and Application Properties before and after the Synthesis.

In this study, the AEOnBO2 series of block polyoxybutenol ethers was synthesized by combining the AEO series of polyoxyethylene and preparing 1,2-epoxybutane (BO) block polyether using a semicontinuous method. The synthesis was performed by HPLC, MALDI-TOF-MS, FT-IR, and 1H NMR for structural analysis. The interaction parameters and surface tension of the systems before and after synthesis were studied using surface tension meter. The diffusion process of the systems before and after synthesis was studied using a KRÜSS bubble pressure tensiometer. The surfactant properties of AEOn and AEOnBO2 were evaluated by static and dynamic surface tension measurements. Each system formed a saturated adsorption layer in a water solution. The critical micelle concentration decreased dramatically after the introduction of BO groups, and the diffusion-adsorption process was consistent with the kinetic mechanism of hybrid diffusion. The microscopic self-assembled aggregate micellar behavior of all the systems was investigated using DLS, TEM, and SEM. The micellization process in all systems was spontaneous and enthalpy-driven, forming spherical aggregates, with the BO block reducing the aggregate diameter of the feedstock from 220.06 nm to about one-third of 80.02 nm. In addition, the dynamic contact angle, application, and physicochemical properties such as foaming and foam stabilization of each system were investigated. The contact angle was reduced from 70 to 50° at 120 s of stabilization, with a foam volume of 80 mL in all systems at 200 s. However, the AEOnBO2 showed accelerated foam decay at 500 s, with an increase in the contact angle from 70 to 50° at 200 s, but the AEOnBO2 showed accelerated foam decay at 500 s, with a decrease in the contact angle from 70 to 50° at 120 s stabilization. At 200 s, the foam volume of all systems was 80 mL, but AEOnBO2 showed an accelerated foam decay process, which shows that the BO group can accelerate the foam decay, and the comparative results show that the BO group can also optimize other application properties and physicochemical properties.

ESIPT+TICT-Based Near-IR Detection of Al3+ and F- in Live Cells: Molecular Docking with Acetylcholinesterase.

The interplay of ESIPT+TICT mechanisms in 1,8-naphthalimide-hydroxyquinoline (NQ-OH) molecular rotor were reported for the near-IR 'turn-on' emission (λmax 600 nm) and ratiometric (A405nm/A345nm) absorbance-based detection of Al3+ ions in aqueous medium and live cells which were supported by NMR, IR and CV techniques. The limit of detection (LOD) for Al3+ ions is 100 nM and 14.57 nM. The self-assembled spherical aggregates of NQ-OH transformed into cuboidal aggregates upon coordination with Al3+ ions supported by microscopic and dynamic light scattering (DLS) techniques. The complex NQ-OH+Al3+ was further used for the secondary detection of F- ions in aqueous medium via displacement approach with LOD as low as 2.67 nM. A deeper study revealed that the NQ-OH is a solvatochromic dye. Probably, the NQ-OH either in the aggregated state or in the coordination state with Al3+ ions, showed an increase in the emission intensity at 600 nm due to inhibition of the ESIPT process and trigger of the TICT process. We have demonstrated the utility of NQ-OH for the detection of Al3+ ions and NQ-OH+Al3+ complex for the detection of F- ions in MCF7 live cells. We have also discussed the molecular docking studies of NQ-OH with acetylcholinesterase enzyme.

Formation of self-assembled fibril aggregates of trypsin-controllably hydrolyzed soy protein and its regulation on stability of high internal phase Pickering emulsions

The mechanisms of trypsin hydrolysis time on the structure of soy protein hydrolysate fibril aggregates (SPHFAs) and the stability of SPHFAs-high internal phase Pickering emulsions (HIPPEs) were investigated. SPHFAs were prepared using soy protein hydrolysate (SPH) with different trypsin hydrolysis time (0 min–120 min) to stabilize SPHFAs-HIPPEs. The results showed that moderate trypsin hydrolysis (30 min, hydrolysis degree of 2.31 %) induced SPH unfolding and increased the surface hydrophobicity of SPH, thereby promoting the formation of flexible SPHFAs with maximal thioflavin T intensity and ζ-potential. Moreover, moderate trypsin hydrolysis improved the viscoelasticity of SPHFAs-HIPPEs, and SPHFAs-HIPPEs remained stable after storage at 25 °C for 80 d and heating at 100 °C for 1 h. Excessive trypsin hydrolysis (> 30 min) decreased the stability of SPHFAs-HIPPEs. In conclusion, moderate trypsin hydrolysis promoted the formation of flexible SPHFAs with high surface charge by inducing SPH unfolding, thereby promoting the stability of SPHFAs-HIPPEs.

Spontaneous Photonic Jammed Packing of Core-Shell Colloids in Conductive Aqueous Inks for Non-Iridescent Structural Coloration.

Integrating structural colors and conductivity into aqueous inks has the potential to revolutionize wearable electronics, providing flexibility, sustainability, and artistic appeal to electronic components. This study aims to introduce bioinspired color engineering to conductive aqueous inks. Our self-assembly approach involves mixing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with sulfonic acid-modified polystyrene (sPS) colloids to generate non-iridescent structural colors in the inks. This spontaneous structural coloration occurs because PEDOT:PSS and sPS colloids can self-assemble into core-shell structures and reversibly cluster into photonic aggregates of maximally random jammed packing within the aqueous environment, as demonstrated by small-angle X-ray scattering. Dissipative particle dynamics simulation confirms that the self-assembly aggregation of PEDOT:PSS chains and sPS colloids can be manipulated by the polymer-colloid interactions. Utilizing the finite-difference time-domain method, we demonstrate that the photonic aggregates of the core-shell colloids achieve close to maximum jammed packing, making them suitable for producing vivid structural colors. These versatile conductive inks offer adjustable color saturation and conductivity, with conductivity levels reaching 36 S cm-1 through the addition of polyethylene glycol oligomer, while enhanced water resistance and mechanical stability are achieved by doping with a cross-linker, poly(ethylene glycol) diglycidyl ether. With these unique features, the inks can create flexible, patterned circuits through processes like coating, writing, and dyeing on large areas, providing eco-friendly, visually appealing colors for customizable, stylish, comfortable, and wearable electronic devices.

Oleanolic acid derivative self-assembled aggregates based on heparin and chitosan for breast cancer therapy

Oleanolic acid is an active ingredient from natural products with anti-breast cancer activity. However, the poor solubility in water and low bioavailability have limited its effectiveness in clinic. To improve the anticancer activity of oleanolic acid, we synthesized a novel oleanolic quaternary ammonium (QDT), which, driven by electrostatic interactions, was introduced into heparin and coated with chitosan to obtain a QDT/heparin/chitosan nanoaggregate (QDT/HEP/CS NAs). QDT/HEP/CS NAs showed the negative zeta potential (−35.01 ± 4.38 mV), suitable mean particle size (150.45 ± 0.68 nm) with strip shape, and high drug loading (36 %). The coated chitosan had strong anti-leakage characteristics toward QDT under physiological conditions. More importantly, upon sustained release in tumor cells, QDT could significantly decrease the mitochondrial membrane potential and induce apoptosis of breast cancer cells. Further in vivo antitumor study on 4 T1 tumor-bearing mice confirmed the enhanced anticancer efficacy of QDT/HEP/CS NAs via upregulation of caspase-3, caspase-9 and cytochrome C, which was attributed to the high accumulation in tumor via the enhanced permeability and retention effect. Moreover, QDT/HEP/CS NAs significantly enhanced the biosafety and biocompatibility of QDT in vitro and in vivo. Collectively, the development of QDT/HEP/CS NAs with high antitumor activity, favorable biodistribution and good biocompatibility provided a safe, facile and promising strategy to improve the anti-cancer effect of traditional Chinese medicine ingredients.

Nontoxic and proteolytic-resistant self-assembled peptide dendrimer aggregates to combat multidrug-resistant gram-negative bacterial infections

Peptide-based antimicrobial biomaterials hold considerable promise to treat the prevalent infections caused by multidrug-resistant (MDR) pathogens. However, their clinical translation is hampered by high toxicity, proteolytic degradation, and poorly understood in vivo efficacy. Here, we present a novel multi-functional blocks intelligent combination approach to create low-toxicity and proteolytic-resistant self-assembled peptide dendrimer aggregates (SPDAs) that exhibit low-micromolar activity (≤4 μM) against gram-negative bacteria and MDR Escherichia coli. We investigated the in vivo biosafety of SPDAs and found that they were substantially less systemically toxic than polymyxin B at the same dose. In a peritonitis-sepsis mouse model, the SPDAs demonstrated significant in vivo therapeutic potential for the treatment of MDR E. coli infections. Importantly, the antimicrobial activity of the SPDAs was exerted via multimodal mechanism that included rapid plasma membrane rupture, interference with cellular growth and metabolism, and triggering reactive oxygen species accumulation. Collectively, SPDAs show tremendous promise in addressing the prevalent infections caused by MDR gram-negative pathogens, and these findings may offer unique insights that will inspire the development of novel peptide-based therapeutics.

Dynamic interfacial adsorption and emulsifying performance of self-assembled coconut protein and fucoidan mixtures

The functional properties of protein are affected by their aggregation behavior and morphology. In this study, the self-assembled coconut protein aggregates with specific morphology, including small amorphous aggregates (WLA), spherical-like aggregates (SLA) and rod-like aggregates (RLA), were regulated to form. The self-assembled process resulted in a decrease in fluorescence intensity and an increase in the surface hydrophobicity of coconut protein. Fucoidan was added to improve the stability of protein solutions, and the interfacial adsorption behavior was evaluated by dilatational rheology analysis. The results showed that the aggregation state of coconut protein affected its ability to reduce surface tension, and the interfacial layers mainly exhibited elastic property at oil-water interface (tanφ < 0.5). For macroscale analysis, the emulsions based on self-assembled coconut protein exhibited smaller droplet size, better rheological properties and centrifugal stability, especially WLA and RLA. This study may provide a reference to inspire the utilization of self-assembled coconut protein in the food industry.

Indazole-5-amine (AIA) as competing corrosion coating to Benzotriazole (BTAH) at the interface of Cu: A DFT and BOMD case study

This study compares three organic compounds—benzotriazole (BTAH), imidazole (IM), and indazole-5-amine (AIA)—as corrosion inhibitors for copper substrates. Using Density Functional Theory (DFT) and Born-Oppenheimer Molecular Dynamics (BOMD) calculations, it identifies AIA as a promising and cost-effective alternative to the toxic BTAH. The adsorption strength on Cu(100) surfaces is ranked AIA>BTAH>IM for both neutral and deprotonated forms. These findings are supported by electronic parameter studies, including Bader charge analysis, density of states (DOS), charge density differences (CDD), and frontier molecular orbital analysis. AIA shows the best adsorption in a parallel orientation at the top site. Packing studies reveal that hydrogen bonding stabilizes the interaction energies within self-assembled AIA aggregates. Organometallic complexation studies reveal that deprotonated BTAH exhibits higher interaction energy with a single Cu atom compared to AIA when bonded through the carbon end, consistent with the findings from BOMD studies. However, on periodic Cu surfaces, AIA outperforms BTAH molecules as seen from adsorption energies. This investigation highlights AIA’s potential as a superior and more economical corrosion inhibitor for copper.

Delivery of Lutein by Using Modified Burdock Polysaccharide Aggregates: Preparation, Characterization, and In Vitro Release Properties.

Novel self-assembled aggregates of stearic acid (SA)-modified burdock polysaccharide (BP) for loading lutein were constructed, and the release and absorption properties of lutein in the aggregates in simulated gastrointestinal fluid were investigated. Three different degrees of substitution (DS) of SA-BPs were used to embed lutein, resulting in the encapsulation efficiency exceeding 90%. The aggregates were uniformly spherical, with a particle size range of 227-341 nm. XRD analysis revealed that lutein was present in a non-crystalline state within the aggregates. FT-IR and FS analysis demonstrated that lutein was located in the hydrophobic domains of SA-BP. The highest bioavailability of lutein in these aggregates reached 4.36 times that in the unmodified samples. These aggregates were able to remain stable in gastric juice and enhance the release rate of lutein in intestinal fluid. The transport of lutein-loaded SA-BP aggregates in Caco-2 cells competed with P-glycoprotein inhibitors, mainly promoting the transmembrane absorption of lutein through caveolae (or lipid raft)-related and clathrin-dependent endocytosis pathways. The above results suggest that SA-BP aggregates have the potential to be promising carriers for the efficient delivery of hydrophobic lutein.

Preparation and characterization of hydrophobically-modified sodium alginate derivatives as carriers for fucoxanthin

Micelles are nano-architectured structures capable of encapsulating hydrophobic substances in aqueous solutions, thereby improving their stability, solubility, and bioavailability to control the release of bioactive compounds. In this study, the sodium alginate backbone was modified via a hydrophobic modification scheme where octyl chains were covalently attached to the alginate chains via esterification reactions. Fourier-transformed infrared spectrometry (FTIR), 1H nuclear magnetic resonance (1H NMR), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA) were used to characterize the structure of the sodium alginate derivatives of varying molar mass (ALG-C8). Fluorescence spectroscopy, surface tension measurements, and dynamic light scattering (DLS) were employed to assess the self-assembly performance of ALG-C8. The three methods produced consistent results, indicating that self-assembly decreased with higher molar mass. The self-assembled ALG-C8 micelles were utilized to encapsulate fucoxanthin. The loading capacity (LC) and encapsulation efficiency (EE) were determined using UV–Vis spectrophotometry. The molar mass of ALG-C8 has a key influence on fucoxanthin loading and release behavior. The ALG-C8 molecules with the lowest molar mass produced micelles with the smallest hydration diameter, resulting in the highest LC and EE. Furthermore, the release of fucoxanthin is significantly influenced by the pH and ionic strength of the medium. ALG-C8 micellar-like aggregates exhibit resistance to low pH and high ionic strength environments, releasing encapsulated material at the target site under alkaline conditions. Therefore, synthesized ALG-C8 is a potential candidate for preparing pH-responsive self-assembled micellar-like aggregates, enabling targeted delivery and gradual release of hydrophobic functional food components.

N-Hydroxyalkanamide Based Organo/hydrogels as Novel Scaffolds for pH-Dependent Metronidazole and Theophylline Release.

The traditional delivery of metronidazole and theophylline presents challenges like bitter taste, variable absorption, and side effects. However, gel-based systems offer advantages including enhanced targeted drug delivery, minimized side effects, and improved patient compliance, effectively addressing these challenges. Consequently, a cost-effective synthesis of N-hydroxyalkanamide gelators with varying alkyl chain lengths was achieved in a single-step reaction procedure. These gelators formed self-assembled aggregates in DMSO/water solvent system, resulting in organo/hydrogels at a minimum gelation concentration of 1.5 % w/v. Subsequently, metronidazole and theophylline were encapsulated within the gel core and released through gel-to-sol transition triggered by pH variation at 37 °C, while maintaining the structural-activity relationship. UV-vis spectroscopy was employed to observe the drug release behavior. Furthermore, in vitro cytotoxicity assays revealed cytotoxic effects against A549 lung adenocarcinoma cells, indicating anti-proliferative activity against human lung cancer cells. Specifically, the gel containing theophylline (16HAD+Th) exhibited cytotoxicity on cancerous A549 cells with IC50 values of 19.23±0.6 μg/mL, followed by the gel containing metronidazole (16HAD+Mz) with IC50 values of 23.75±0.7 μg/mL. Moreover, the system demonstrated comparable antibacterial activity against both gram-negative (E. coli) and gram-positive bacteria (S. aureus).

Cosolvents effect on supercritical CO2 microemulsion containing ionic Liquid: Experiment and simulation

Supercritical carbon dioxide (scCO2) microemulsion containing ionic liquids (ILs) 1-ethyl-3-methylimidazolium acetate ([Emim]Ac) were prepared under mild operating conditions with the help of surfactant branched secondary alcohol ethoxylates (TMN-6) and cosolvents (water and ethanol). Phase equilibrium experiments and molecular dynamics (MD) simulations were conducted from gas-phase system, two-phase system to supercritical system. The conditions of constructing supercritical microemulsion were studied by using self-made phase equilibrium device. The effects of temperature, surfactant concentration, and cosolvent concentration on cloud point pressure (CPP) were studied. The results showed that the transparent and uniform microemulsion could not be formed in gas-phase and two-phase systems. In supercritical system, the proper addition of cosolvent water and ethanol contributed to the formation of microemulsion and the dissolution of ILs. However, the reduction effect of CPP was not obvious or even increased when only water was added. After added water and ethanol simultaneously, not only did the maximum WIL increase to 0.26, but CPP also significantly decreased. MD simulation was conducted to characterize the microstructure of three systems. Furthermore, the gyration radius, radial distribution function (RDF), and hydrogen bond dynamics were calculated to analyze the strengthening mechanism of cosolvents on self-assembly. The simulation results revealed that, water promoted the interaction between hydrophilic groups of surfactants and ionic liquids, while ethanol constructed a hydrogen bonding network between continuous and dispersed phases. Water and ethanol have synergistic effect on the preparation of supercritical microemulsion, which has a good effect on improving the self-assembly rate and aggregate stability.

Exploring the Synthesis of Self-Organization and Active Motion.

Proteins, genetic material, and membranes are fundamental to all known organisms, yet these components alone do not constitute life. Life emerges from the dynamic processes of self-organization, assembly, and active motion, suggesting the existence of similar artificial systems. Against this backdrop, our Perspective explores a variety of chemical phenomena illustrating how nonequilibrium self-organization and micromotors contribute to life-like behavior and functionalities. After explaining key terms, we discuss specific examples including enzymatic motion, diffusiophoretic and bubble-driven self-propulsion, pattern-forming reaction-diffusion systems, self-assembling inorganic aggregates, and hierarchically emergent phenomena. We also provide a roadmap for combining self-organization and active motion and discuss possible outcomes through biological analogs. We suggest that this research direction, deeply rooted in physical chemistry, offers opportunities for further development with broad impacts on related sciences and technologies.

Direct electrospinning for producing multiple activity nanofibers consisting of aggregated luteolin/hydroxypropyl-gamma-cyclodextrin inclusion complex

Hydroxypropyl-gamma-cyclodextrin (HPγCD) inclusion complex nanofibers (Lut/HPγCD-IC-NF) containing Luteolin (Lut) were prepared by electrospinning technology. Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) spectra confirmed the formation of Lut/HPγCD-IC-NF. Scanning electron microscopy (SEM) images showed that the morphology of Lut/HPγCD-IC-NF was uniform and bead-free, suggesting that self-assembled aggregates, macromolecules with higher molecular weights, were formed by strong hydrogen bonding interactions between the cyclodextrin inclusion complexes. Confocal laser scanning microscopy (CLSM) images showed that Lut was distributed in Lut/HPγCD-IC-NF. Proton nuclear magnetic resonance (1H NMR) spectroscopy revealed the change in chemical shift of the proton peak between Lut and HPγCD, confirming the formation of inclusion complex. Thermogravimetric analysis (TGA) proved that Lut/HPγCD-IC-NF had good thermal stability. The phase solubility test confirmed that HPγCD had a solubilizing effect on Lut. When the solubility of HPγCD reached 10 mM, the solubility of Lut increased by 15-fold. The drug loading test showed that the content of Lut in fibers reached 8.57 ± 0.02 %. The rapid dissolution experiment showed that Lut/HPγCD-IC-NF dissolved within 3 s. The molecular simulation provides three-dimensional evidence for the formation of inclusion complexes between Lut and HPγCD. Antibacterial experiments showed that Lut/HPγCD-IC-NF had enhanced antibacterial activity against S. aureus. Lut/HPγCD-IC-NF exhibited excellent antioxidant properties with a free radical scavenging ability of 89.5 ± 1.1 %. In vitro release experiments showed Lut/HPγCD-IC-NF had a higher release amount of Lut. In conclusion, Lut/HPγCD-IC-NF improved the physicochemical properties and bioavailability of Lut, providing potential applications of Lut in the pharmaceutical field.

Asymmetric Aldol Reactions Catalyzed by Polymeric Self-Assembly with Side-Chain Dipeptide Pendants.

To explore the role of proline amide moieties in polymer-supported organocatalysts, side-chain l-proline-l-alanine (Pro-Ala) dipeptide-containing block copolymers were synthesized, and their catalytic potential for the aldol reaction was explored. The dipeptide monomer (Boc-Pro-Ala-HEMA) was polymerized to prepare block copolymers in the presence of hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA) and hydrophobic poly(methyl methacrylate) (PMMA) macro-chain transfer agents. Boc group expulsion from the block copolymers produced double hydrophilic PPEGMA-b-P(Pro-Ala-HEMA) (1b) and amphiphilic PMMA-b-P(Pro-Ala-HEMA) (1c) polymers. The solution behaviors of the polymers were studied by various physical techniques, which showed the formation of self-assembled aggregates of 1c in water and N,N-dimethylformamide (DMF)/water solvent mixtures. These polymers are used as organocatalysts during the aldol reaction of cyclohexanone and 4-nitrobenzaldehyde in different solvent polarities, catalyst loadings, temperatures, and reaction times. This work emphasizes superior catalytic activity of 1c at lower catalyst loadings (5%) while maintaining high conversion (95%) and enantioselectivity (94%) across multiple recycling cycles in DMF/water at a 3:1 ratio (v/v).

Nanofibrous polyelectrolyte complex incorporated BSA-alginate composite bioink for 3D bioprinting of bone mimicking constructs

Although several bioinks have been developed for 3D bioprinting applications, the lack of optimal printability, mechanical properties, and adequate cell response has limited their practical applicability. Therefore, this work reports the development of a composite bioink consisting of bovine serum albumin (BSA), alginate, and self-assembled nanofibrous polyelectrolyte complex aggregates of gelatin and chitosan (PEC-GC). The nanofibrous PEC-GC aggregates were prepared and incorporated into the bioink in varying concentrations (0 % to 3 %). The bioink samples were bioprinted and crosslinked post-printing by calcium chloride. The average nanofiber diameter of PEC-GC was 62 ± 15 nm. It was demonstrated that PEC-GC improves the printability and cellular adhesion of the developed bioink and modulates the swelling ratio, degradation rate, and mechanical properties of the fabricated scaffold. The in vitro results revealed that the bioink with 2 % PEC-GC had the best post-printing cell viability of the encapsulated MG63 osteosarcoma cells and well oragnized stress fibers, indicating enhanced cell adhesion. The cell viability was >90 %, as observed from the MTT assay. The composite bioink also showed osteogenic potential, as confirmed by the estimation of alkaline phosphatase activity and collagen synthesis assay. This study successfully fabricated a high-shape fidelity bioink with potential in bone tissue engineering.

Efficient and accurate binding free energy calculation of Aβ9-40 protofilament propagation.

Self-assembled aggregation of peptides and proteins into regular amyloid fibrils is associated with several neurodegenerative diseases. In case of Alzheimer's disease proteolytic cleavage products of the amyloid precursor protein form pathological amyloid-beta fibrils in a nucleation and propagation phase. The molecular details and thermodynamic driving forces of amyloid formation are not well understood, but are of high relevance for potential pharmacological interference. We used atomistic binding free energy simulations to calculate the free energy of protofilament propagation by an additional Aβ9-40 peptide binding to the protofilament tip. It requires sampling of relevant conformational transitions which is challenging since the monomeric Aβ9-40 peptide is intrinsically disordered. However, the convergence of umbrella simulations can be enhanced by applying additional restraining potentials on the axial, orientational and conformational degrees of freedom. The improved convergence leads to a much closer agreement with experimental binding free energy data compared to unrestrained umbrella sampling. Moreover, the restraining approach results in a separation of contributions to the total binding free energy. The calculated contributions indicate that the free energy change associated with the restriction of conformational freedom upon propagation makes a large opposing contribution of higher magnitude than the total binding free energy. Finally, optimization of the approach leads to further significant reduction of the computational demand which is crucial for systematic studies on mutations, denaturants and inhibitors in the fibril propagation step.

Regulation of Fluorescence and Self-assembly of a Salicylaldehyde Azine-Containing Amphiphile by Pillararene.

Regulation of fluorescence and self-assembly of a salicylaldehyde azine-containing amphiphile by a water-soluble pillar[5]arene via host-guest recognition in water was realized. The fluorescence and the self-assembled aggregates of the bola-type amphiphile G can be tailored by adding different amounts of water-soluble pillar[5]arene (WP5). In addition, the emission property and self-assembly behavior of G and WP5 are responsive to pH conditions. Furthermore, the fluorescence emission property of G and the regulation by WP5 or pH conditions was applied as information encryption material, rewritable paper, and erasable ink. We believe that this fluorescence regulation strategy is promising for the construction of advanced fluorescent organic materials.