Self-assembly of Monosaccharide Derivatives

Monosaccharides, the fundamental molecular units of carbohydrates, are central to biological recognition, energy conversion, and structural functions in living systems. Their inherent chirality gives rise to a wide range of stereoisomers, which are critical for both biological recognition and molecular self-assembly. Despite their fundamental significance, the supramolecular organization of monosaccharides remains comparatively underexplored, especially relative to well-studied self-assembling systems such as peptides and oligonucleotides. This thesis investigates the stereochemical configuration and targeted chemical modification direct the organization and control self-assembly pathways of monosaccharide assemblies, particularly the transition from metastable intermediates to thermodynamically stable structures. The self-assembly behavior analysis among sugar azides reveals a spontaneous bending-to-straightening behavior, accompanied by helical deformation, via amorphous-crystalline solid transformation. Bending-to-straightening behavior is vital for both natural processes and advanced materials design. Nonclassical crystallization pathways, such as amorphous-crystalline transformation, present promising avenues for realizing unique actuation. The process commences with a bending amorphous nanowire, which grows into locally crystallized nanoribbon with twist, and finally form a straight crystalline rectangular hollow tube via screw dislocation. Depending on the synergy between the stereostructure of the sugar skeleton and the collinear dipole arrangement of the azide group, the initial helical amorphous aggregation and a directional shift in growth priorities can be regulated during the bending-to-straightening behavior. It offers valuable insights into the design of spontaneous bending-to-straightening behavior and its potential applications in colonizing unstructured environments. Building on the understanding of self-assembly dynamics, the second part addresses chiral evolution and attenuation in a glucose derivative, α-D-glucose pentabenzoate (GluP). Controlled chiral amplification mediated by nanofiber entanglement has attracted substantial attention. However, the progression of chiral architecture toward thermodynamic stable in dynamic systems remains insufficiently explored. This progression, whether rapid or gradual, critically defines the temporal window for application and determines the ultimate functional capacity of such systems. We investigate such progression during the hierarchical self-assembly of GluP, which undergoes a transition from left-handed helical chiral nanofibers to superhelix nanofiber bundles, and ultimately to unexpected achiral microfibers formed by nanofiber entanglement. This transformation, driven by a shift from disordered amorphous packing to an ordered crystalline state, involves a distinct conformational rearrangement and a transition from weaker local helical stacking to more compact, parallel-displaced π–π interactions with reduced inter-ring distances. Moreover, the in solution born GluP superstructured nanofiber network can be applied on micro/nanoparticles disposal. A sustainable, closed-loop strategy for the disposal of micro/nanoparticles (N/MPs) in solution, termed In situ nanofiber growth-wrapping-disposal (INGWD), was developed. The INGWD approach exhibits remarkable adaptability, effectively processing diverse metal-based and polymeric N/MPs across a wide size range (approx. 5 nm to 1 μm) and a broad pH range (3–12). This robust method performs exceptionally in both aqueous and alcoholic carriers, achieving maximum N/MP removal and monosaccharide derivative recycling efficiencies of 99.47% and 99.07%, respectively. The performance of the INGWD strategy is highlighted by a maximum N/MP wrapping capacity of approximately 2 g·g⁻¹. These results establish INGWD as a versatile platform for N/MP disposal, offering promising potential for sustainable separation, recycling, and underwater applications. This thesis is a cumulative work comprising three publications. One of them has already been accepted, while the remaining two were being prepared for submission. The background, the objective of the study, results and discussion of the three publications and the conclusions are presented in Section 1-4.