Computer Simulation of Template Polymerization Using a Controlled Reaction Scheme

Datta, Preeta; Genzer, Jan

doi:10.1021/ma3025915

Cited by 8 publications

(10 citation statements)

References 29 publications

(54 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Note that these numbers for packing density are calculated relative to the maximum occupancy of bound monomers on a square lattice. As in case of 1D substrates described previously, varying the concentration of free A monomers does not have an effect of the system behavior except for increasing the molecular weight of the polymers. This is due to the large excess of A monomers present in the system.…”

Section: Results and Discussion: Computer Simulationmentioning

confidence: 99%

“…The Monte Carlo (MC) simulation scheme, based on the Bond Fluctuation Model (BFM), 22 was used to model the "living"/ controlled radical polymerization in case of a 2D substrate, as described in our earlier publication. 21 The substrates, monomers, and polymers reside on a 3D cubic lattice, with the substrate forming the base of the simulation box. The B monomers are bound covalently to the planar substrate, hence their positions are held fixed throughout the simulation.…”

Section: Set-up and Methodsmentioning

confidence: 99%

“…Our system is "truly living", i.e., the chains do not undergo termination of chain transfer. 21 The implicit solvent model (i.e., no explicit solvent molecules are included in the simulations) is presumed to be valid for modeling the growth of "living" chains under good solvent conditions. 23,24 The initiator molecules and free monomers are originally distributed homogeneously throughout the lattice.…”

Section: Set-up and Methodsmentioning

confidence: 99%

“…Periodic boundary conditions were applied in only in the X and Y directions along the plane of the substrate. As described in our earlier publication, the values of the parameters intrinsic to the MC simulation scheme are held constant at the same values during all the runs.…”

Section: Computer Simulationmentioning

confidence: 99%

“…Our previous work discussed “grafting through” on one‐dimensional (1D) substrates. This is perhaps the simplest geometry to model and understand as it imposes the least restriction on the polymer chains.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

“Grafting through” polymerization involving surface‐bound monomers

Datta

Genzer

2015

J. Polym. Sci. Part A: Polym. Chem.

Self Cite

View full text Add to dashboard Cite

"Grafting through" polymerization represents copolymerization of free monomers in solution and polymerizable units bound to a substrate. Free polymer chains are formed initially in solution and can incorporate the surface-bound monomers, and thereby, get covalently bonded to the surface during the polymerization process. As more growing chains attach to the surfacebound monomers, an immobilized polymer layer is formed on the surface. We use a combination of computer simulation and experiments to comprehend this process for monomers bound to a flat impenetrable substrate. We concentrate specifically on addressing the effect of spatial density of the surface-bound monomers on the formation of the surface-attached polymers. We employ a lattice-based Monte Carlo model utilizing the bond fluctuation model scheme to provide molecular-level insight into the grafting process. For experimental validation, we create gradients of density of bound methacrylate units on flat silicon wafers using organosilane chemistry and carry out "grafting through" free radical polymerization initiated in bulk. We report that the proximity of the surface-bound polymerizable units promotes the "grafting through" process but prevents more free growing chains to "graft through'' the polymerizable units. The "grafting through" process is self-limiting in nature and does not affect the overall density of the surface-bound polymer layer, except in case of the highest theoretical packing density of surface-bound monomers.

show abstract

Section: Results and Discussion: Computer Simulationmentioning

confidence: 99%

Section: Set-up and Methodsmentioning

confidence: 99%

Section: Set-up and Methodsmentioning

confidence: 99%

Section: Computer Simulationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

“Grafting through” polymerization involving surface‐bound monomers

Datta

Genzer

2015

J. Polym. Sci. Part A: Polym. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

Controlled Grafting Expansion Microscopy

et al. 2023

View full text Add to dashboard Cite

Expansion microscopy (ExM) is a recently developed technique that allows for the resolution of structures below the diffraction limit by physically enlarging a hydrogel‐embedded facsimile of the biological sample. The target structure is labeled and this label must be retained in a relative position true to the original, smaller state before expansion by linking it into the gel. However, gel formation and digestion lead to a significant loss in target‐delivered label, resulting in weak signal. To overcome this problem, we have here developed an agent combining targeting, fluorescent labeling and gel linkage in a single small molecule. Similar approaches in the past have still suffered from significant loss of label. Here we show that this loss is due to insufficient surface grafting of fluorophores into the hydrogel and develop a solution by increasing the amount of target‐bound monomers. Overall, we obtain a significant improvement in fluorescence signal retention and our new dye allows the resolution of nuclear pores as ring‐like structures, similar to STED microscopy. We furthermore provide mechanistic insight into dye retention in ExM.

show abstract

Controlled Grafting Expansion Microscopy

et al. 2023

View full text Add to dashboard Cite

Expansion microscopy (ExM) is a recently developed technique that allows for the resolution of structures below the diffraction limit by physically enlarging a hydrogel-embedded facsimile of the biological sample. The target structure is labeled and this label must be retained in a relative position true to the original, smaller state before expansion by linking it into the gel. However, gel formation and digestion lead to a significant loss in target-delivered label, resulting in weak signal. To overcome this problem, we have here developed an agent combining targeting, fluorescent labeling and gel linkage in a single small molecule. Similar approaches in the past have still suffered from significant loss of label. Here we show that this loss is due to insufficient surface grafting of fluorophores into the hydrogel and develop a solution by increasing the amount of target-bound monomers. Overall, we obtain a significant improvement in fluorescence signal retention and our new dye allows the resolution of nuclear pores as ring-like structures, similar to STED microscopy. We furthermore provide mechanistic insight into dye retention in ExM.

show abstract

Computer Simulation of Template Polymerization Using a Controlled Reaction Scheme

Cited by 8 publications

References 29 publications

“Grafting through” polymerization involving surface‐bound monomers

“Grafting through” polymerization involving surface‐bound monomers

Controlled Grafting Expansion Microscopy

Controlled Grafting Expansion Microscopy

Contact Info

Product

Resources

About