Backbone Stiffness Research Articles

Multiscale Analyses of Strain-Enhanced Charge Transport in Conjugated Polymers.

The advancement of flexible and wearable electronics relies on semiconducting polymers that can endure mechanical deformation while maintaining high electrical performance under strain. In this study, we demonstrate that fine-tuning backbone rigidity through the molecular design of donor moieties significantly enhances both the mechanical and charge transport properties of diketopyrrolopyrrole (DPP)-based polymers. Specifically, the flexible DPP-4T (quaterthiophene) exhibited a persistence length of 20.4 nm in solution, while DPP-DTT (dithienothiophene) showed a longer persistence length of 32.8 nm due to its stiff backbone, as confirmed by small-angle neutron scattering and Monte Carlo simulations. This flexibility enabled DPP-4T to achieve a crack-onset strain exceeding 100% via the film-on-elastomer method and a fracture strain of over 30% in quasi-free-standing films. Additionally, DPP-4T demonstrated a 180% increase in hole mobility at 80% strain, driven by strain-induced chain alignment and backbone planarization. Utilizing a range of characterization techniques, including ultraviolet-visible (UV-vis) spectroscopy, grazing incidence X-ray diffraction (XRD), and Raman spectroscopy, we characterized structural changes at multiple length scales under applied tensile strain. Notably, strain induced a transformation in chain conformation from a twisted to a flat structure, reducing the hopping energy barrier and enhancing charge transport. These structural rearrangements are crucial for sustaining efficient charge transport and ensuring the reliability of electronic performance under mechanical stress.

Understanding the role of chain stiffness in the mechanical response of cross-linked polymer: Flexible vs. semi-flexible chains

Cross-linked polymers are widely used in structural, engineering, and biomedical applications due to their lightweight and superior properties. Although chain bending stiffness has been recognized to play an essential role in their thermodynamical and mechanical properties, how it influences these properties of cross-linked polymers with flexible or semi-flexible chains remains under debate. Here, we systematically explore its influences utilizing coarse-grained (CG) molecular dynamics (MD) simulations based on a bead-spring CG model. It is found that with chain bending stiffness increasing, both density and elastic moduli (i.e., shear modulus and tensile modulus) of cross-linked polymers first decrease slightly and then decrease significantly followed by a gradual increase, along with the polymer transition from a dense cross-linked thermoset to a highly porous fibrous network. The moduli of cross-linked polymers with flexible and semi-flexible chains exhibit distinct scaling laws with the density. For cross-linked polymers with flexible chains, their moduli increase significantly with increasing strain rate, which correlates to the change in potential energy of interchain interaction during deformation. However, the moduli display slight dependence on strain rate for porous cross-linked polymers with sufficiently stiff chains, where the intrachain interactions (i.e., bond stretching and angle bending energies) become dominant and independent of strain rate. Moreover, the elastic moduli exhibit scaling laws with Debye-Waller factor for both dense cross-linked thermosets with flexible chains and highly porous networks with stiff backbones. Our work facilitates a better understanding for mechanical properties and deformation mechanism of cross-linked polymers with variable chain bending stiffness at molecular level, shedding light on tailoring mechanical properties of cross-linked polymers via chain engineering.

Seismic response assessment of ductile reinforced concrete columns affected by corrosion and axial load variations

The present study investigates the effect of reinforcement corrosion and axial compression ratio (ACR) on the seismic response of large-scale ductile reinforced concrete (RC) columns. 3D numerical models of sound and corroded RC columns were developed and validated with detailed experimentation. Various parameters, such as hysteresis and backbone curves, stiffness degradation, ductility, and energy dissipation, were evaluated for all the specimens. The numerical findings were then compared with the experimental findings. Subsequently, a thorough parametric study was executed to analyse the structural behaviour under varying corrosion degrees and ACR level combinations. It was observed that both sound and corroded specimens experienced significant degradation in terms of their strength, deformability, stiffness, and ductility due to elevated ACR levels. Moreover, increased ACR levels in both specimen types led to a decline in pre-peak and post-peak response trajectories, resulting in an early achievement of peak response at lower drift levels. The study’s outcome advocates the significance of incorporating ACR levels into the design philosophy of ductile reinforcements for RC columns.

Cylinders-in-Undulating-Lamellae Morphology from ABC Bottlebrush Block Terpolymers.

Block polymer self-assembly affords a versatile bottom-up strategy to develop materials with the desired properties dictated by specific symmetries and dimensions. Owing to distinct properties compared with linear counterparts, bottlebrush block polymers with side chains densely grafted on a backbone have attracted extensive attention. However, the morphologies found in bottlebrush block polymers so far are limited, and only lamellar and cylindrical ordered phases have been reported in diblock bottlebrushes. The absence of complex morphologies, such as networks, might originate from the intrinsically stiff backbone architecture. We experimentally investigated the morphologies of nonfrustrated ABC bottlebrush block terpolymers, based on two chemistries, poly(ethylene-alt-propylene)-b-polystyrene-b-poly(dl-lactic acid) (PEP-PS-PLA) and PEP-b-PS-b-poly(ethylene oxide) (PEP-PS-PEO), synthesized by ring-opening metathesis polymerization of norbornene-terminated macromonomers. Structural characterization based on small-angle X-ray scattering and transmission electron microscopy measurements revealed an unprecedented cylinders-in-undulating-lamellae (CUL) morphology with p2 symmetry for both systems. Additionally, automated liquid chromatography was employed to fractionate the PEP-PS-PLA bottlebrush polymer, leading to fractions with a spectrum of morphologies, including the CUL. These findings underscore the significance of macromolecular dispersity in nominally narrow dispersity bottlebrush polymers while demonstrating the power of this fractionation technique.

Reversed dynamics of bottlebrush polymers with stiff backbone and flexible side chains.

The segmental dynamics of bottlebrush polymers with a stiff backbone and flexible side chains has been studied. The segmental relaxation time of side chains attached to a flexible backbone follows the same trend as linear polymers, an increase with the increasing molecular weight, but is slowed down compared to their linear counterparts. Theoretical work predicts a reversal of the molecular weight dependence of the relaxation time for stiff backbones. As a model for a stiff-g-flexible system, bottlebrushes with poly(norbornene) backbone and poly(propylene oxide) side chains, PNB-g-PPO, at a uniform grafting density have been synthesized and characterized with quasi-elastic neutron scattering. Indeed, the anticipated reversed dynamics was found. Increasing the side chain length decreases the segmental relaxation time. This indicates the importance of the characteristics of the grafting site beyond a simplified picture of an attached side chain. The mean square displacement shows a similar trend with longer side chains exhibiting a larger displacement.

Thermal Conductivity of Bottle-Brush Polymers.

Using molecular dynamics (MD) simulations of a generic model, we investigated heat propagation in bottle-brush polymers (BBP). An architecture is referred to as a BBP when a linear (backbone) polymer is grafted with the side chains of different length Ns and grafting density ρg, which control the bending stiffness of a backbone. Investigating κ-behavior in BBP is of particular interest due to two competing mechanics: increased backbone stiffness, via Ns and ρg, increases the thermal transport coefficient κ, while the presence of side chains provides additional pathways for heat leakage. We show how a delicate competition between these two effects controls κ. These results reveal that going from a weakly grafting (ρg < 1) to a highly grafting (ρg ≥ 1) regime, κ changes non-monotonically that is independent of Ns. The effect of side chain mass on κ and heat flow in the BBP melts is also discussed.

A Compliant Hinge Joint Driven by the PneuNets Bending Actuator

AbstractWhile soft robots enjoy the benefits of high adaptability and safety, their inherent flexibility makes them suffer from low load-carrying capacity and motion precision, which limits their applications to a broader range of fields. To address this problem, we propose a novel compliant hinge joint with a stiff backbone for load-carrying coupled with soft pneumatic networks (PneuNets) bending actuators. We derive a pseudo-rigid-body model of the joint design and validate it through experiments and simulations. The results show that the joint can achieve a large range of bending angles. The off-axis stiffness is from 16.74 to 627.63 times the in-axis stiffness. This design can carry a heavy load off-axis while maintaining the in-axis flexibility. This work lays out the foundation for designing high-performance soft robots by combining various flexure mechanisms and pneumatic bending actuators.

Xylan-cellulose core structure of oat water-extractable β-glucan macromolecule: Insight into interactions and organization of the cell wall complex

Water-extractable β-glucan with high molar mass (HM) determines health benefits of oat food. Oat β-glucan was extracted by a standardized in vitro digestion method and co-existing water-extractable polysaccharide (WEP) fraction and its HM-arabinoxylan (HM-AX) subfraction were isolated to identify their highly acid-resistant subunit and investigate molecular interactions between constituent polymers. The WEP and HM-AX samples consisted of arabinoxylans (AXs) (74 and 76 %, respectively), however, cellulose constituted the secondary component (6.6 and 12.8 %, respectively). Multi-detection HPSEC along with specific enzymatic hydrolysis of AXs revealed the presence of the HM-xylan domain (16 and 34 %, respectively) built of numerous single- and multi-component populations with random coil and rod-like conformations, which were embedded in a xylan matrix with spherical conformation and controlled the macromolecular shape. Unlike single-component populations, the multi-component ones were resistant to hydrolytic action of AX-hydrolyzing enzymes and represented the subunits that anchor matrix polysaccharides onto cellulose surface. These results indicate that water-extractable β-glucan macromolecule comprises as integral element a cellulose core with two linking populations, HM-xylan and low molar mass glucomannan, which are surrounded by a feruloylated AX-arabinan-arabinogalactan composite and next laminated by β-glucan matrix. The stiff cellulose-xylan backbone is the basis of HM β-glucan organization, controlled by its cellulose-like segments.

Zinc Anodes with Electrodeposited Ionomer Protection Layer for Rechargeable Zinc-Air Batteries

Metal air batteries are assembled from a metal anode and a porous cathode in a suitable electrolyte. They combine the design of fuel cells and conventional batteries and have been demonstrated to have large theoretical energy densities higher compared to devices based on Li-ion chemistry, due to the ability to use air at the cathode and to exchange two electrons per zinc atom. ZAB represent a safe, environmentally benign, affordable and simple way to store and deliver electrical energy for a wide variety of devices. However, research efforts are necessary to increase the efficiency of rechargeable ZAB and mitigate obnoxious occurrences that decrease the number of charge-discharge cycles such as zinc dendrite formation, cathode degradation and alkaline electrolyte carbonation.The protection of zinc metal anodes in zinc-air batteries (ZAB) is an efficient way to reduce corrosion and Zn dendrite formation and improve cyclability and overall battery efficiency. The extent of improvement depends on the type and thickness of the protective layer.In this work, we explore an advanced coating of the zinc anode by anion-conducting poly(N-vinylbenzyl, N,N,N trimethylammonium) chloride (PVBTMA) that is electropolymerized directly on the zinc metal. The Zn deposition in presence of quaternary ammonium salts and polyelectrolytes was recently studied to improve the cyclability. The major advances foreseen by this approach are excellent qualities of the metal/ionomer interface, due to the in-situ deposition process, improving the corrosion protection and the selective anion permeability; furthermore, the chosen ionomer presents a high stiffness and strength to resist the formation of zinc dendrites, due to the stiff polystyrene backbone. Moreover, the presence of a polyelectrolyte separator facilitates device miniaturization. The zinc anode protection layer was observed by optical microscopy and scanning electron microscopy (Figure : SEM micrographs of Zn pellet with PVBTMA layer: a) from 0.01 M precursor solution, b) and c) from 0.1 M precursor solution) .and the wettability of the ionomer-coated zinc surface was investigated by contact angle measurements.The resulting ZAB battery with PVBTMA anode coating is analyzed in terms of cyclability in alkaline electrolyte and solid-state configuration using a Whatman paper separator.The goal is to pair metal-free electrode materials with appreciable catalytic activity for oxygen reduction and evolution with a zinc anode that has a protection layer against dendrite formation to maximize efficiency. Figure 1

Lightweight Pneumatically Elastic Backbone Structure with Modular Construction and Nonlinear Interaction for Soft Actuators.

There has been a growing need for soft robots operating various force-sensitive tasks due to their environmental adaptability, satisfactory controllability, and nonlinear mobility unique from rigid robots. It is of desire to further study the system instability and strongly nonlinear interaction phenomenon that are the main influence factors to the actuations of lightweight soft actuators. In this study, we present a design principle on lightweight pneumatically elastic backbone structure (PEBS) with the modular construction for soft actuators, which contains a backbone printed as one piece and a common strip balloon. We build a prototype of a lightweight (<80 g) soft actuator, which can perform bending motions with satisfactory output forces (∼20 times self-weight). Experiments are conducted on the bending effects generated by interactions between the hyperelastic inner balloon and the elastic backbone. We investigated the nonlinear interaction and system instability experimentally, numerically, and parametrically. To overcome them, we further derived a theoretical nonlinear model and a numerical model. Satisfactory agreements are obtained between the numerical, theoretical, and experimental results. The accuracy of the numerical model is fully validated. Parametric studies are conducted on the backbone geometry and stiffness, balloon stiffness, thickness, and diameter. The accurate controllability, operation safety, modularization ability, and collaborative ability of the PEBS are validated by designing PEBS into a soft laryngoscope, a modularized PEBS library for a robotic arm, and a PEBS system that can operate remote surgery. The reported work provides a further applicability potential of soft robotics studies.

Polyelectrolyte Cylindrical Brushes in Hairy Gels.

We considered dispersions of cylindrical polyelectrolyte (PE) brushes with stiff backbones, and polymer-decorated nanorods with tunable solubility of the brush-forming PE chains that affected thermodynamic stability of the dispersions. We focused on thermo-induced and deionization-induced conformational transition that provokes loss of aggregative dispersion stability of nanorods decorated with weakly ionized polyions. A comparison between theoretical predictions and experiments enabled rationalization and semi-quantitative interpretation of the experimental results.

Unexpected Slow Relaxation Dynamics in Pure Ring Polymers Arise from Intermolecular Interactions.

Ring polymers have fascinated scientists for decades, but experimental progress has been challenging due to the presence of linear chain contaminants that fundamentally alter dynamics. In this work, we report the unexpected slow stress relaxation behavior of concentrated ring polymers that arises due to ring-ring interactions and ring packing structure. Topologically pure, high molecular weight ring polymers are prepared without linear chain contaminants using cyclic poly(phthalaldehyde) (cPPA), a metastable polymer chemistry that rapidly depolymerizes from free ends at ambient temperatures. Linear viscoelastic measurements of highly concentrated cPPA show slow, non-power-law stress relaxation dynamics despite the lack of linear chain contaminants. Experiments are complemented by molecular dynamics (MD) simulations of unprecedentedly high molecular weight rings, which clearly show non-power-law stress relaxation in good agreement with experiments. MD simulations reveal substantial ring-ring interpenetrations upon increasing ring molecular weight or local backbone stiffness, despite the global collapsed nature of single ring conformation. A recently proposed microscopic theory for unconcatenated rings provides a qualitative physical mechanism associated with the emergence of strong inter-ring caging which slows down center-of-mass diffusion and long wavelength intramolecular relaxation modes originating from ring-ring interpenetrations, governed by the onset variable N/ND, where the crossover degree of polymerization ND is qualitatively predicted by theory. Our work overcomes challenges in achieving ring polymer purity and by characterizing dynamics for high molecular weight ring polymers. Overall, these results provide a new understanding of ring polymer physics.

Enabling Long-Lived Polymeric Room Temperature Phosphorescence Material in Abominable Solvent.

Long-lived polymeric room temperature phosphorescence (RTP) materials have drawn more attention due to their convenient preparation process and equally efficient phosphorescence performance in recent years. As the polymer matrix is sensitive to air and humidity, some non-covalent interactions in the matrix are easily decomposed in water or air, which means that it is difficult for this material to be stored stably for a long time in the atmospheric environment or under harsh conditions. In this work, polymer powder mBPipQ contains aromatic and piperidine rings that are designed and synthesized successfully. Then the polymer is uniformly dispersed into epoxy resin matrix to form long-lived polymeric RTP material with efficient afterglow properties. The stiff backbone structure of mBPip and dense molecular arrangement of epoxy resin provide a rigid environment to stabilize triplet excitons, the RTP performance is greatly enhanced. The lifetime of mBPipQ in epoxy resin is 2 times higher than that of small molecule chromophore in that one. Interestingly, after soaking in strong acid or alkali solution for 10 days, the material can still emit stable and efficient long-lived phosphorescence. It is thanks to the hard matrix after full curing, which can provide a protective layer to prevent external quenchers from interfering with phosphorescence emission. Utilizing the efficient phosphorescence emission and excellent abominable-solvent resistance of this RTP material, multilevel information encryption has been successfully demonstrated. This work broadens the application scope of polymeric RTP materials in harsh environments and provides a new idea for achieving efficient RTP emission.

Flow-induced buckling of elastic microfilaments with non-uniform bending stiffness

Buckling plays a critical role in the transport and dynamics of elastic microfilaments in Stokesian fluids. However, previous work has only considered filaments with homogeneous structural properties. Filament backbone stiffness can be non-uniform in many biological systems like microtubules, where the association and disassociation of proteins can lead to spatial and temporal changes into structure. The consequences of such non-uniformities in the configurational stability and transport of these fibers are yet unknown. Here, we use slender-body theory and Euler-Bernoulli elasticity coupled with various non-uniform bending rigidity profiles to quantify this buckling instability using linear stability analysis and Brownian simulations. In shear flows, we observe more pronounced buckling in areas of reduced rigidity in our simulations. These areas of marked deformations give rise to differences in the particle extra stress, indicating a non-trivial rheological response due to the presence of these filaments. The fundamental mode shapes arising from each rigidity profile are consistent with the predictions from our linear stability analysis. Collectively, these results suggest that non-uniform bending rigidity can drastically alter fluid-structure interactions in physiologically relevant settings, providing a foundation to elucidate the complex interplay between hydrodynamics and the structural properties of biopolymers.

Side Chain Dynamics of Poly(norbornene)-g-Poly(propylene oxide) Bottlebrush Polymers.

The segmental dynamics of the side chains of poly(norbornene)-g-poly(propylene oxide) (PNB-g-PPO) bottlebrush polymer in comparison to PPO is studied by quasi-elastic neutron scattering. Having experimental time and length scale information simultaneously allows to extract spatial information in addition to relaxation time. Tethering one end of the PPO side chain onto a stiff PNB backbone slows down the segmental relaxation, over the length and time scales investigated. The power law dependence of the relaxation time on the momentum transfer, Q, indicates a more heterogeneous relaxation pattern for the bottlebrush polymer, whereas the linear PPO has less deviations from a homogenous relaxation. Similar conclusions can be drawn from the time dependent mean square displacement, 〈r2 (t)〉, and the non-Gaussian parameter, α2 (t). Herein, the bottlebrush polymer shows a more restricted dynamics, whereas the linear PPO reaches 〈r2 (t)〉∝t0.5 at the highest temperature. The deviations from Gaussian behavior are evident at the α2 (t). Both samples show a decaying α2 (t). The non-Gaussian parameter supports the results from the power law dependence of the relaxation times, with lower α2 (t) values for PPO compared to those for PNB-g-PPO, pointing to less deviations from Gaussian behavior.

Cylindrical brushes with ionized side chains: Scaling theory revisited.

We revisit the classic scaling model of a cylindrical polyelectrolyte (PE) brush focusing on molecular brushes with stiff backbones and dispersions of polymer-decorated nanorods. Based on the blob representation we demonstrate that similarly to the case of planar PE brushes, separation of intra- and intermolecular repulsions between charges leads to novel scaling regimes for cylindrical PE brushes in salt-added solution and a sharper decrease in its thickness versus salt concentration dependence. These theoretical predictions may inspire further comprehensive experimental research and computer simulations of synthetic and biopolyelectrolyte cylindrical brushes.

An Amorphous n‐Type Conjugated Polymer with an Ultra‐Rigid Planar Backbone

AbstractHigh charge carrier mobility polymer semiconductors are always semi‐crystalline. Amorphous conjugated polymers represent another kind of polymer semiconductors with different charge transporting mechanism. Here we report the first near‐amorphous n‐type conjugated polymer with decent electron mobility, which features a remarkably rigid, straight and planar polymer backbone. The molecular design strategy is to copolymerize two fused‐ring building blocks which are both electron‐accepting, centrosymmetrical and planar. The polymer is the alternating copolymer of double B←N bridged bipyridine (BNBP) unit and benzobisthiazole (BBTz) unit. It shows a decent electron mobility of 0.34 cm2 V−1 s−1 in organic field‐effect transistors. The excellent electron transporting property of the polymer is possibly due to the ultrahigh backbone stiffness, small π‐π stacking distance, and high molecular weight.

An Amorphous n-Type Conjugated Polymer with an Ultra-Rigid Planar Backbone.

High charge carrier mobility polymer semiconductors are always semi-crystalline. Amorphous conjugated polymers represent another kind of polymer semiconductors with different charge transporting mechanism. Here we report the first near-amorphous n-type conjugated polymer with decent electron mobility, which features a remarkably rigid, straight and planar polymer backbone. The molecular design strategy is to copolymerize two fused-ring building blocks which are both electron-accepting, centrosymmetrical and planar. The polymer is the alternating copolymer of double B←N bridged bipyridine (BNBP) unit and benzobisthiazole (BBTz) unit. It shows a decent electron mobility of 0.34 cm2 V-1 s-1 in organic field-effect transistors. The excellent electron transporting property of the polymer is possibly due to the ultrahigh backbone stiffness, small π-π stacking distance, and high molecular weight.

Contact-based molecular dynamics of structured and disordered proteins in a coarse-grained model: Fixed contacts, switchable contacts and those described by pseudo-improper-dihedral angles

We present a coarse-grained Cα-based protein model that can be used to simulate structured, intrinsically disordered and partially disordered proteins. We use a Go-like potential for the structured parts and two different variants of a transferable potential for the disordered parts. The first variant uses dynamic structure-based (DSB) contacts that form and disappear quasi-adiabatically during the simulation. By using specific structural criteria we distinguish sidechain-sidechain, sidechain-backbone and backbone-backbone contacts. The second variant is a non-radial multi-body pseudo-improper-dihedral (PID) potential that does not include time-dependent terms but requires more computational resources. Our model can simulate in reasonable time thousands of residues on millisecond time scales. Program summaryProgram Title: cgCPC Library link to program files:https://doi.org/10.17632/dp7gwrs94n.1Code Ocean capsule:https://codeocean.com/capsule/9528010Licensing provisions: MITProgramming language: C++ (new version), Fortran (old version)Nature of problem: Simulations of one or more protein chains, structured, intrinsically disordered or partially disordered. Calculating their equilibrium and kinetic properties in processes including but not limited to: folding, aggregation, conformational changes, formation of complexes, aggregation, response to deformation. All those processes need long simulation times or many trajectories to properly sample the system.Solution method: The simulations use a molecular dynamics implicit-solvent coarse-grained model where each pseudoatom represents one amino acid residue. Residues are harmonically connected to form a chain. The system evolves according to Langevin dynamics. The backbone stiffness potential involves bond angle and dihedral angle terms (or a chirality term in the structured case). Residues interact via modified Lennard-Jones or Debye-Hueckel potentials.The potential is different for structured and disordered parts of a protein. A Go model contact map is used for the structured parts, where an interaction between two residues is attractive if effective spheres associated with their heavy atoms overlap in the native structure [1,2,3,4]. Non-attractive contacts use only the repulsive part of the Lennard-Jones potential. The potential for the disordered parts has two versions: in the quasi-adiabatic Dynamic Structure-Based (DSB) variant, the contacts are formed dynamically based on the structure of the chain and are quasi-adiabatically turned on and off [5,6]. In the slower, but more accurate Pseudo-Improper-Dihedral (PID) variant the Lennard-Jones term is multiplied by a pseudo-improper-dihedral term that gives similar geometric restrictions with a time-independent Hamiltonian [7].Proteins can be pulled by their termini to mimic stretching by an Atomic Force Microscope [8,9]. Multiple protein chains can be put in a simulation box with periodic boundary conditions or with walls that may be repulsive or attractive for the residues. The walls may move to mimic pulling or shearing deformations. The program accepts PDB files or protein sequences with optional user-defined contact maps. It saves the results in an output file (summary), a PDB file (structure) and a map file (contact map in a given snapshot).Additional comments including restrictions and unusual features: The program supports openMP (effective up to 8 cores, use 4 cores for optimal speed-up). The C++ version is hosted on Github, the Fortran version is distributed as a .tar archive.

How Cooperatively Folding Are Homopolymer Molecular Knots?

Detailed thermodynamic analysis of complex systems with multiple stable configurational states allows for insight into the cooperativity of each individual transition. In this work we derive a heat capacity decomposition comprising contributions from each individual configurational state, which together sum to a baseline heat capacity, and contributions from each state-to-state transition. We apply this analysis framework to a series of replica exchange molecular dynamics simulations of linear and 1-1 coarse-grained homo-oligomer models which fold into stable, configurationally well-defined molecular knots, in order to better understand the parameters leading to stable and cooperative folding of these knots. We find that a stiff harmonic backbone bending angle potential is key to achieving knots with specific 3D structures. Tuning the backbone equilibrium angle in small increments yields a variety of knot topologies, including $3_1$, $5_1$, $7_1$, and $8_{19}$ types. Populations of different knotted states as functions of temperature can also be manipulated by tuning backbone torsion stiffness or by adding side chain beads. We find that sharp total heat capacity peaks for the homo-oligomer knots are largely due to a coil-to-globule transition, rather than a cooperative knotting step. However, in some cases the cooperativity of globule-to-knot and coil-to-globule transitions are comparable, suggesting that highly cooperative folding to knotted structures can be achieved by refining the model parameters or adding sequence specificity.