Self-assembly Of Polymer Chains Research Articles

Deposition patterns formed by the evaporation of linear diblock copolymer solution nanodroplets on solid surfaces.

The evaporation-induced deposition pattern of the linear diblock copolymer solution has attracted attention in recent years. Given its critical applications, we study deposition patterns of the linear diblock copolymer solution nanodroplet on a solid surface (the wall) by molecular dynamics simulations. This study focuses on the influence of the nonbonded interaction strength, including the interaction between the wall and polymer blocks (ɛAW and ɛBW), the interaction between the solvent and the wall (ɛSW), and the interaction between polymer blocks (ɛAB). Conditions leading to diverse deposition patterns are explored, including the coffee-ring and the volcano-like structures. The formation of the coffee-ring structure is attributed to receding interfaces, the heterogeneity inside the droplet, and the self-assembly of polymer chains. This study contributes to the establishment of guidelines for designing deposition patterns of the linear diblock copolymer solution nanodroplet, which facilitates practical applications such as inkjet printing.

Advanced treatment and reuse of dye wastewater using thermo-irreversible on/off switch starch with disruption of dissolution/precipitation dynamic equilibrium

The development of irreversible on/off switching materials is a potential strategy for unidirectional capture and encapsulation of pollutants, preventing the pollutant leakage problem resulting from the reversible dissolution of flocculants. Herein, a thermo-irreversible on/off switch starch (TISS) is prepared through modifying starch by etherification grafting glycidyl phenyl ether and 2,4-bis(dimethylamino)-6-chloro-[1,3,5]-triazine. It breaks the dissolution/precipitation dynamic equilibrium across heating–cooling cycles by thermal-induced irreversible coil-to-globule self-assembly of polymer chains, resulting in a 50-fold decrease in polymer solubility. Particularly, TISS shows a superior double-locking effect on pollutants and flocculants through its unique irreversible conformation memory capability, leading to a high-quality reuse water. 99.9 % of reactive brilliant red dye and 97.9 % of TISS remain fixed within sludge flocs even after prolonged immersion in cold water at 24 °C for 60 days. Furthermore, direct recycling and reuse of dye-bath energy can be realized through the isothermal flocculation and dyeing method, showing a 75 % decrease in energy consumption after three cycles compared to traditional dyeing techniques. This work presents a novel approach to constructing an irreversible pollutant delivery system using thermo-irreversible on/off switch starch, addressing the problems of high energy dissipation and water quality fluctuations during wastewater treatment.

N-Substituted Benzene-1-Urea-3,5-Biscarboxamide (BUBA): Easily Accessible C2 -Symmetric Monomers for the Construction of Reversible and Chirally Amplified Helical Assemblies.

Non-C3 -symmetric supramolecular helices are gaining interest for the design of hierarchical assemblies, for the compartmentalisation or the self-assembly of polymer chains and for application in asymmetric catalysis. Herein, N-substituted benzene-1-urea-3,5-biscarboxamide (BUBA) monomers, which consist of one urea and two carbon-connected amide functions linked to an aromatic ring, are introduced as an easily accessible class of C2 -symmetric supramolecular synthons. In apolar solvents, BUBA monomers assemble into long helical assemblies by means of hydrogen-bonding and aromatic interactions, as assessed by several analytical techniques. To probe the influence of the urea function, BUBA and related benzene-1,3,5-tricarboxamide (BTA) helical polymers have been compared, in terms of their thermodynamics of formation, stability, reversibility and chiral amplification properties. Similar to BTA, BUBA monomers form long helices reversibly through a highly cooperative mechanism and the helicity of their assemblies is governed by chiral amplification effects. However, precise quantification of their properties reveals that BUBA monomers assemble in a more cooperative manner. Also, chiral amplification operates to a higher extent in BUBA helices, as probed by both sergeants-and-soldiers and majority-rules experiments. Compatibility between urea and amide functions also allows the formation of co-assemblies that incorporate both BUBA and BTA monomers. Importantly, a small amount of chiral BUBA monomers in these co-assemblies is sufficient to obtain single-handed helices; thus paving the way towards the development of functional supramolecular helices.

Cross-Linking Induced Self-Organization of Polymers into Degradable Assemblies.

Covalently stabilized polymer assemblies are normally fabricated from the self-assembly of polymer chains followed by a cross-linking reaction. In this report, we show that a cross-linking-induced self-assembly approach, in which boronate cross-linking sites are formed by the condensation reaction between boronic and catechol groups, can organize polymer networks into uniform assemblies. Self-assembly of these boronate cross-linked polymer networks adopts two different driving forces in water and methanol solutions. Hydrophobic aggregation of polymer networks in water solution affords spherical assemblies, while B-N dative bond formed between boronate and imine functionalities in methanol solution organizes the polymer networks into bundle-like assemblies. We not only demonstrate the intrinsic stimuli-responsive degradability of these cross-linked assemblies but also show that their degradation can cause a controllable release of guest molecules. Moreover, bundle-like assemblies with rough surface and exposed boronate functionalities exhibit dramatically higher cell penetration capability than the spherical assemblies with smooth surface and embedded boronate functionalities.

Fast formation of ripples induced by AFM. A new method for patterning polymers on nanoscale

The possibility to control the assembly of molecules on a given substrate is particularly important for polymeric systems. Self-assembly of polymer chains on a substrate can be controlled by modifying selectively the chemistry of the substrate surface and/or the polymer itself in order to create patterned polymer films with tailored length scales. A novel tool to change the polymer morphology in order to achieve the requested superficial structures and textures is the atomic force microscopy (AFM). In this paper, we shall demonstrate how to obtain ordered ripple structures induced by an AFM tip on a polymer thin film. It is well known that a polymer surface scanned by a probe tip can change its morphology assuming typical ripple structures. These structures however are expected to be formed for high applied loads (> 10 nN) and after many scanning cycles (> 10). On the contrary, we shall show how to obtain the ripple formation just by a single AFM scan and for relatively low applied loads. Such ripple structures can be modulated and modified by changing the applied load, scanning velocity and angle. In this way, it is possible to obtain sinusoidal structures with suitable amplitude, periodicity and orientation. Beyond the general contribution to the development of nanolithography, the patterns obtained by this method can find many applications in biomaterial polymer science (such as scaffolds for cell proliferation in tissue engineering).