RESUMO
Understanding and control of the effective interaction between nanoscale building blocks (colloids or nanoparticles) dispersed in a solvent is an important prerequisite for the development of bottom-up design strategies for soft functional materials. Here, we have employed all-atom molecular dynamics simulations to investigate the impact of polymer grafting on the solvent-mediated effective interaction between the silica nanoparticles (Si-NPs) in water, and in turn, on its bulk structural and thermodynamic properties. We found that the nature of the short grafting polymers [characterized by their interaction with water (hydrophobicity or hydrophilicity) and molecular weight] has a profound effect on the range and strength of the effective interaction between the Si-NPs. The hydrophobic polymer [such as polyethylene (PE)]-grafting of Si-NP gives rise to a more attractive interaction between the Si-NPs compared to the hydrophilic polymer [such as polyethylene glycol (PEG)] and non-grafted cases. This study further provides fundamental insights into the molecular origin of the observed behavior of the effective pair interactions between the grafted Si-NPs. For PE-grafted Si-NPs, the confined water (water inside the cavity formed by a pair of Si-NPs) undergoes a partial dewetting transition on approaching below a critical inter-particle separation leading to a stronger attractive interaction. Furthermore, we report that the effective attraction between the PE-grafted Si-NPs can be reliably controlled by changing the grafting PE density. We have also investigated the bulk structural and thermodynamic behavior of the coarse-grained Si-NP system where the particles interact via effective interaction in the absence of water. We believe that the insights gained from this work are important prerequisites for formulating rational bottom-up design strategies for functional materials where nano- (or, colloidal) particles are the building blocks.
RESUMO
Covalent organic nanosheets (CONs) have emerged as functional two-dimensional materials for versatile applications. Although π-π stacking between layers, hydrolytic instability, possible restacking prevents their exfoliation on to few thin layered CONs from crystalline porous polymers. We anticipated rational designing of a structure by intrinsic ionic linker could be the solution to produce self-exfoliated CONs without external stimuli. In an attempt to address this issue, we have synthesized three self-exfoliated guanidinium halide based ionic covalent organic nanosheets (iCONs) with antimicrobial property. Self-exfoliation phenomenon has been supported by molecular dynamics (MD) simulation as well. Intrinsic ionic guanidinium unit plays the pivotal role for both self-exfoliation and antibacterial property against both Gram-positive and Gram-negative bacteria. Using such iCONs, we have devised a mixed matrix membrane which could be useful for antimicrobial coatings with plausible medical benefits.
Assuntos
Anti-Infecciosos/química , Guanidina/química , Nanoestruturas/química , Modelos Moleculares , Simulação de Dinâmica MolecularRESUMO
Using dissipative particle dynamics, we characterize dynamics of aggregation of molecular bottlebrushes in solvents of various qualities by tracking the number of clusters, the size of the largest cluster, and an average aggregation number. We focus on a low volume fraction of bottlebrushes in a range of solvents and probe three different cutoff criteria to identify bottlebrushes belonging to the same cluster. We demonstrate that the cutoff criteria which depend on both the coordination number and the length of the side chain allows one to correlate the agglomeration status with the structural characteristics of bottlebrushes in solvents of various qualities. We characterize conformational changes of the bottlebrush within the agglomerates with respect to those of an isolated bottlebrush in the same solvents. The characterization of bottlebrush conformations within the agglomerates is an important step in understanding the relationship between the bottlebrush architecture and material properties. An analysis of three distinct cutoff criteria to identify bottlebrushes belonging to the same cluster introduces a framework to identify both short-lived transient and long-lived agglomerates; the same approach could be further extended to characterize agglomerates of various macromolecules with complex architectures beyond the specific bottlebrush architecture considered herein.
RESUMO
Controlling morphology of polysiloxane blends crosslinked by the hydrosilylation reaction followed by pyrolysis constitutes a robust strategy to fabricate polymer-derived ceramics (PDCs) for a number of applications, from water purification to hydrogen storage. Herein, we introduce a dissipative particle dynamics (DPD) approach that captures the phase separation in binary and ternary polymer blends undergoing hydrosilylation. Linear polyhydromethylsiloxane (PHMS) chains are chosen as preceramic precursors and linear vinyl-terminated polydimethylsiloxane (v-PDMS) chains constitute the reactive sacrificial component. Hydrosilylation of carbon-carbon unsaturated double bonds results in the formation of carbon-silicon bonds and is widely utilized in the synthesis of organosilicons. We characterize the dynamics of binary PHMS/v-PDMS blends undergoing hydrosilylation and ternary blends in which a fraction of the reactive sacrificial component (v-PDMS) is replaced with the non-reactive sacrificial component (methyl-terminated PDMS (m-PDMS), polyacrylonitrile (PAN), or poly(methyl methacrylate) (PMMA)). Our results clearly demonstrate that the morphology of the sacrificial domains in the nanostructured polymer network formed can be tailored by tunning the composition, chemical nature, and the degree of polymerization of the sacrificial component. We also show that the addition of a non-reactive sacrificial component introduces facile means to control the self-assembly and morphology of these nanostructured materials by varying the fraction, degree of polymerization, or the chemical nature of this component.
RESUMO
We fabricated thermoplastic surfaces possessing extremely limited water and oil wettability without employment of long-chain perfluoroalkyl (LCPFA) substances. Namely, by taking advantage of the structure and behavior of original oleophobic perfluoropolyether (PFPE) methacrylate (PFM) molecular bottlebrush (MBB) additive we obtained polymeric surfaces with oil contact angles well above 80° and surface energy on the level of 10 mN/m. Those angles and surface energies are the highest and the lowest respective values reported to date for any bulk solid flat organic surface not containing LCPFA. We show experimentally and computationally that this remarkable oil repellency is attributed to migration of small quantities of the oleophobic MBB additives to the surface of the thermoplastics. Severe mismatch in the affinity between the densely grafted long side chains of MBB and a host matrix promotes stretching and densification of mobile side chains delivering the lowest surface energy functionalities (CF3) to the materials' boundary. Our studies demonstrate that PFM can be utilized as an effective low surface energy additive to conventional thermoplastic polymers, such as poly(methyl methacrylate) and Nylon-6. We show that films containing PFM achieve the level of oil repellency significantly higher than that of polytetrafluoroethylene (PTFE), a fully perfluorinated thermoplastic. The surface energy of the films is also significantly lower than that of PTFE, even at low concentrations of PFM additives.
RESUMO
A novel heteroditopic ion-pair receptor was synthesized by tethering two π-acidic naphthalenediimide units with a tridentate bisimine linker. Upon chelating a ZnII or CdII ion with the linker, it adopts a U-conformation allowing the parallel NDI arms to sandwich charge-diffuse anions, and two such folded receptor molecules interlock with each other forming an [R3·MII·R3·X-] ion-pair complex. Extraction of the guest cation with a tetraazacrown ether returns the receptor to its original unfolded form.