Backbone Segments Research Articles

Reprocessable Polymer Networks Containing Sulfur-Based, Percolated Dynamic Covalent Cross-Links and Percolated or Non-Percolated, Static Cross-Links.

One method to improve the properties of covalent adaptable networks (CANs) is to reinforce them with a fraction of permanent cross-links without sacrificing their (re)processability. Here, a simple method to synthesize poly(n-hexyl methacrylate) (PHMA) and poly(n-lauryl methacrylate) (PLMA) networks containing static dialkyl disulfide cross-links (utilizing bis(2-methacryloyl)oxyethyl disulfide, or DSDMA, as a permanent cross-linker) and dynamic dialkylamino sulfur-sulfur cross-links (utilizing BiTEMPS methacrylate as a dissociative dynamic covalent cross-linker) is presented. The robustness and (re)processability of the CANs are demonstrated, including the full recovery of cross-link density after recycling. The authors also investigate the effect of static cross-link content on the stress relaxation responses of the CANs with and without percolated, static cross-links. As PHMA and PLMA have very different activation energies of their respective cooperative segmental mobilities, it is shown that the dissociative CANs without percolated, static cross-links have activation energies of stress relaxation that are dominated by the dissociation of BiTEMPS methacrylate cross-links rather than by the cooperative relaxations of backbone segments, i.e., the alpha relaxation. In CANs with percolated, static cross-links, the segmental relaxation of side chains, i.e., the beta relaxation, is critical in allowing for large-scale stress relaxation and governs their activation energies of stress relaxation.

Anti-Quenching NIR-II Excitation Phenylboronic Acid Modified Conjugated Polyelectrolyte for Intracellular Peroxynitrite-Enhanced Chemo-Photothermal Therapy.

Multidrug resistance to clinical chemotherapeutic drugs severely limits antitumor efficacy and patient survival. The integration of chemotherapy with photothermal therapy (PTT) and reactive nitrogen species has become a major strategy to enhance cancer treatment efficacy. Herein, a multifunctional peroxynitrite (ONOO-) nanogenerator (PBT/NO/Pt) for NIR-II fluorescence (NIR-II FL)/NIR-II photoacoustic (NIR-II PA) imaging-guided chemo/NIR-II PTT/ONOO- combination therapy is reported. The multifunction nanogenerator is developed by co-loading a pH-sensitive nitric oxide donor (DETA NONOate) and nicotinamide adenine dinucleotide phosphate oxidases trigger superoxide (O2 •-) generator chemotherapy drug (CDDP) to an NIR-II excitation-conjugated polyelectrolyte (PNC11BA). PNC11BA has non-conjugated alkyl chain segments in the polymer backbone and abundant positively charged phenylboronic acid in its side chains, which support the anti-quenching of NIR-II FL and the integration of DETA NONOate and CDDP into PBT/NO/Pt. In the acidic tumor microenvironment, the coordination bonds between CDDP and PNC11BA are cleaved, releasing CDDP for chemotherapeutic activity. The simultaneous release of nitric oxide (NO) and O2 •- rapidly leads to the in situ generation of the more cytotoxic reactive physiological nitrogen species ONOO-. In vitro and in vivo results prove that PBT/NO/Pt exhibited a markedly ONOO- enhanced chemo-photothermal synergistic therapy for SKOV3/DDP tumor by downregulating the intracellular glutathione and increasing CDDP-DNA adducts.

Influence of dangling chains on the microphase separation and damping properties of polyurethane

AbstractUnderstanding how dangling fragments of polyurethanes (PU) affect its microphase separation structure and damping properties can provide insights for designing desired materials at the molecular scale. By varying the types of diol extenders (such as 1,2‐ethyleneglycol, 1,2‐propanediol, and 1,2‐butanediol), PU samples with different dangling residues were successfully synthesized. Using atomic force microscopy and small‐angle x‐ray scattering, we confirmed that the introduction of dangling chains disrupts microphase separation and demonstrated a correlation between the degree of suppressed microphase separation and the size of the dangling residues. Fourier transform infrared spectroscopy and molecular dynamics simulations confirmed that dangling chains reduce the hydrogen bonding index while increasing the phase compatibility between soft and hard segments. Differential scanning calorimetry (DSC) measurements revealed an increased glass transition temperature (Tg), indicating hindered movement of backbone segments due to dangling chains. Moreover, lengthening the dangling chains further decreased Tg. Dynamic mechanical analysis (DMA) demonstrated improved damping properties with the introduction of dangling chains, although increasing chain length led to deteriorating damping properties, consistent with observations from DSC. These findings suggest that the variations in macroscopic properties of PU induced by dangling chains are linked to hydrogen bonding interactions and micromorphology at the molecular level.

Impact of a Lightly Branched Star Polyelectrolyte Architecture on Polyelectrolyte Complexes.

The effect of charge density in blocky and statistical linear polyelectrolytes on polyelectrolyte complex (PEC) properties has been studied with the finding that increased charge density in a polyelectrolyte tends to increase the salt resistance and modulus of a PEC across various polyelectrolyte pairs. Here, we demonstrate the ability to orthogonally alter PEC salt resistance while maintaining rheological properties and internal structure by going from linear to lightly branched architectures with similar total degrees of polymerization. Using a model system built around glycidyl methacrylate (GMA) and thiol-epoxy "click" functionalization, we create a library of homologous linear, 4-armed, 6-armed, and 8-armed star polyelectrolytes. The PECs formed from these model polyelectrolyte pairs are then characterized via optical microscopy, rheology, and small-angle X-ray scattering to evaluate their salt resistance, mechanical properties, and internal structure. We argue that our results are due to the difference between linear charge density or charge per unit length along backbone segments for each polyelectrolyte and spatial charge density, the number of charges per unit volume of the polyelectrolyte prior to complexation. Our findings suggest that linear charge density is the dominant factor in determining intermolecular interactions of the complex, leading to identical rheological and structural behavior, whereas the spatial charge density primarily influences the stability of the complexes. These distinct mechanisms for altering various sought-after PEC properties offer greater potential applications in precision design of polyelectrolyte complex materials.

Display Technologies for Expanding the Pharmaceutical Applications of Cyclotides

Display Technologies for Expanding the Pharmaceutical Applications of Cyclotides

On the way to increase osseointegration potential: Sequential SI-ATRP as promising tool for PEEK-based implant nano-engineering

In the search of the ideal bone implant material, surface initiated atom transfer radical polymerization (SI-ATRP) techniques were successfully employed to modify the polyetheretherketone (PEEK) surface with complex architecture nanolayers featuring hydrophilic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) or poly(2-hydroxyethyl methacrylate) (PHEMA) branches. As a result, polymer layers with height up to over 300 nm were synthesized to decrease the water contact angle from 92.8° to 23.0°. In-depth analysis of layer topography, structure and elemental composition realized with atomic force microscopy (AFM), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), time-of-flight secondary ions mass spectroscopy (TOF-SIMS) and X-ray photon spectroscopy (XPS) confirmed successful surface modification. Additionally, to demonstrate the applicability of proposed PEEK functionalization, the biomineralization assay in simulated body fluid (SBF) solution was conducted. The high density of hydroxyl and amine groups in branched polymer brushes structure enhanced the rate of hydroxyapatites (HAp) formation substantially. Compared to untreated PEEK, modification with polymer brushes resulted in the creation of cauliflower-like structures with high specific surface area and Ca/P ratio equal to 1.83–1.87 for PEEK grafted with brushes composed of PHEMA backbone segment and PDMAEMA or PHEMA as block polymer branches (PEEK-g-PHEMA-g-PDMAEMA or PEEK-g-PHEMA-g-PHEMA) after 2 weeks. Finally, the process of the hydroxyapatite formation and increase of the layer thickness in a range of 14 days to 6 weeks of immersion in SBF was thoroughly visualized by scanning electron microscopy (SEM).

Improved Protein Model in SPICA Force Field.

The previous version of the SPICA coarse-grained (CG) force field (FF) protein model focused primarily on membrane proteins and successfully reproduced the dimerization free energies of several transmembrane helices and the stable structures of various membrane protein assemblies. However, that model had limited accuracy when applied to other proteins, such as intrinsically disordered proteins (IDPs) and peripheral proteins, because the dimensions of the IDPs in an aqueous solution were too compact, and protein binding on the lipid membrane surface was overstabilized. To improve the accuracy of the SPICA FF model for the simulation of such systems, in this study, we introduce protein secondary structure-dependent nonbonded interaction parameters to the backbone segments and reoptimize almost all nonbonded parameters for amino acids. The improved FF proposed here successfully reproduces the radii of gyration of various IDPs, the binding sensitivity of several peripheral membrane proteins, and the dimerization free energies of several transmembrane helices. The new model also shows improved agreement with experiments on the free energy of peptide association in water. In addition, an extensive library of nonbonded interactions between proteins and lipids, including various glycerophospholipids, sphingolipids, and cholesterol, allows the study of specific interactions between lipids and peripheral and transmembrane proteins. Hence, the new SPICA FF (version 2) proposed herein is applicable with high accuracy for simulating a wide range of protein systems.

Insight into the chemical transformation and organic release of polyurethane microplastics during chlorination

The ubiquitous occurrence of microplastics in water and wastewater is a growing concern. In this study, the chemical transformation and organic release of virgin and UV-aged thermoplastic polyurethane (TPU) polymers during chlorination were investigated. As compared to virgin TPU polymer, the UV-aged TPU polymer exhibited high chlorine reactivity with noticeable destruction on its surface functional groups after chlorination, which could be ascribed to the UV-induced activation of hard segment of TPU backbone and increased contact area. The concentrations of leached organics increased by 1.6-fold with obviously high abundances of low-molecular-weight components. Additives, monomers, compounds relating to TPU chain extension, and their chlorination byproducts contributed to the increased organic release. Meanwhile, the formation of chloroform, haloacetic acids, trichloroacetaldehyde, and dichloroacetonitrile increased by 3.8-, 1.7-, 4.9-, and 2.4-fold, respectively. Two additives and six chlorination byproducts in leachate from chlorinated UV-aged TPU were predicted as highly toxic, e.g., butyl octyl phthalate, palmitic acid, 2,6-di-tert-butyl-1,4-benzoquinone, and chlorinated aniline. Evaluated by human hepatocarcinoma cells, the 50% lethal concentration factor of organics released from chlorinated UV-aged TPU was approximately 10% of that from its virgin counterpart, indicating a substantially increased level of cytotoxicity. This study highlights that the release of additives and chlorination byproducts from the chemical transformation of UV-aged microplastics during chlorination may be of potentially toxic concern.

Modeling with Alternate Locations in X-ray Protein Structures.

In many molecular modeling applications, the standard procedure is still to handle proteins as single, rigid structures. While the importance of conformational flexibility is widely known, handling it remains challenging. Even the crystal structure of a protein usually contains variability exemplified in alternate side chain orientations or backbone segments. This conformational variability is encoded in PDB structure files by so-called alternate locations (AltLocs). Most modeling approaches either ignore AltLocs or resolve them with simple heuristics early on during structure import. We analyzed the occurrence and usage of AltLocs in the PDB and developed an algorithm to automatically handle AltLocs in PDB files enabling all structure-based methods using rigid structures to take the alternative protein conformations described by AltLocs into consideration. A respective software tool named AltLocEnumerator can be used as a structure preprocessor to easily exploit AltLocs. While the amount of data makes it difficult to show impact on a statistical level, handling AltLocs has a substantial impact on a case-by-case basis. We believe that the inspection and consideration of AltLocs is a very valuable approach in many modeling scenarios.

Assessment of the industry segments functioning of the grain products sub-complex

The solution of the national food problem largely depends on the intensive development of the subcomplex of grain products of the backbone segment of the agro-industrial complex. The priority of this sector of the agro-industrial complex is due to the strategic importance of grain, due to the constant need for it of various agro-food structures and on its basis of food products of the population. In this regard, there is an objective need to substantiate promising directions for the development of the grain products subcomplex, taking into account modern principles of achieving targets. Given the complexity of the socio-economic conditions of the current period, the subcomplex of grain products in the most popular sectors of the national economy is included in the agricultural cluster. In this regard, the priority direction of the national policy is not only to prevent a recession in various sectors of the agricultural sector, but also to ensure an increase in output both to fully meet domestic needs and to increase exports. Such an approach requires the combined efforts of all subjects of the agro-industrial complex, coordination of activities and a purposeful focus on achieving a high final result. The article notes that the development of production in the sectors of the economy of Kazakhstan requires the search and use of new, more effective forms of production and economic activity. One of the main methods of solving this problem is the integration of commodity producers, which allows combining all the links of the reproduction cycle in a single complex in the technological chain “processing of raw materials – production of finished products”.

Geometric constraints within tripeptides and the existence of tripeptide reconstructions.

Designing movesets providing high quality protein conformations remains a hard problem, especially when it comes to deform a long protein backbone segment, and a key building block to do so is the so-called tripeptide loop closure (TLC). Consider a tripeptide whose first and last bonds ( and ) are fixed, and so are all internal coordinates except the six dihedral angles associated to the three carbons. Under these conditions, the TLC algorithm provides all possible values for these six dihedral angles-there exists at most 16 solutions. TLC moves atoms up to in one step and retains low energy conformations, whence its pivotal role to design move sets sampling protein loop conformations. In this work, we relax the previous constraints, allowing the last bond ( ) to freely move in 3D space-or equivalently in a 5D configuration space. We exhibit necessary geometric constraints in this 5D space for TLC to admit solutions. Our analysis provides key insights on the geometry of solutions for TLC. Most importantly, when using TLC to sample loop conformations based on consecutive tripeptides along a protein backbone, we obtain an exponential gain in the volume of the -dimensional configuration space to be explored.

Can Linear Conjugated Polymers Form Stable Helical Structures on the Carbon Nanotubes?

The formation mechanism of ordered helical structures of conjugated polymers wrapping onto single-walled carbon nanotubes (SWCNTs) has been full of controversy in recent decades. A formation mechanism is proposed for the linear conjugated polymers wrapping around SWCNTs that the formation of helical structures is dependent on the orientation competition between backbone segments and side groups via transmission electron microscopy observations and molecular dynamics simulations. Results show that the conjugated polymers cannot always form stable helical structures, even if they have the capability to form a stable helix. In fact, only part of polymer segments presents a stable helix on the SWCNTs for the internal rotation in polymer deformations. Furthermore, a design framework is proposed to choose specific conjugated homopolymers and copolymers which can form helical structures on the SWCNTs.

Exploring highly soluble ether-free polybenzimidazole as anion exchange membranes with long term durability

A series of ether-free polybenzimidazoles (PBIs) containing alicyclic and aliphatic segments were synthesized for the application of anion exchange membranes (AEMs). The PBI-based AEMs prepared in this work (denoted as Pip-PBIs) possessed both high anionic conductivity and alkaline stability by grafting long alkyl chain 1-methylpiperidinium. Benefiting from the random arrangement of aromatic-alicyclic/aliphatic in backbone and their flexible spatial configurations, most Pip-PBIs showed significantly improved solubility in low boiling point solvents namely methanol and isopropanol, which could allow it as ionomer to improve the phase interface between catalyst and AEMs. Meanwhile, the flexible segments in backbone contributed to the formation of ion conductive channel, the Pip-PBI-C achieved the highest hydroxide ions conductivity of 108.8 mS cm −1 at 80 °C, and the conductivity could retain 82.9% after soaking in a 2 M aqueous NaOH at 80 °C for 1536 h. Furthermore, Pip-PBIs demonstrated well oxidation stability in Fenton's reagent (4 ppm FeSO 4 and 3% H 2 O 2 ). Moreover, the H 2 –O 2 fuel cell using Pip-PBI-C as membrane achieved a high open circuit voltage of 1.0 V and a peak power density of 785.6 mW cm −2 at the current density of 1802.9 mA cm −2 . ● A series of polybenzimidazoles containing alicyclic or aliphatic are prepared; ● Pip-PBIs with flexible chain segments have well solubility in low boiling point solvents namely methanol and isopropanol; ● The Pip-PBI-C shows the OH − conductivity of 108.8 mS cm −1 at 80 °C and excellent alkaline stability; ● The Pip-PBI-C shows the peak power density of 785.6 mW cm −2 at 1802.9 mA cm −2 in a H 2 –O 2 fuel cell.

Main-chain side-chain combined liquid crystalline polymers bearing azobenzene and biphenyl-based mesogens – segregation of the mesogens within two distinct layers

ABSTRACT Two different mesogenic units, namely biphenyl and azobenzene, were installed centrally within the polymer backbone and pendant alkylene segments; the purpose was to examine if chain folding of the backbone occurs so as to segregate the azobenzene and biphenyl units in adjacent layers of a smectic-type ordering. Two sets of isomeric main-chain side-chain liquid crystalline polymers (MCSC-LCPs), namely SC-AzoCx-MC-BPCx and SC-BPCx-MC-AzoCx (x=6 or 10), were synthesised; the former series has biphenyl in the backbone and azobenzene in the side-chain, while their locations are switched in the latter. It was observed that all four polymers were semicrystalline at room temperature and exhibited a smectic mesophase upon melting. DSC and X-ray scattering studies revealed that switching the locations of the azobenzene and biphenyls had little effect on; the phase transition temperatures and smectic layer spacings. A second series, namely SC-AzoCx-MC-BPCy and SC-BPCx-MC-AzoCy, where the length of alkylene spacers in the side-chain (Cx) and backbone (Cy) is different, was also studied; this was done to examine the influence of unequal alkylene segment lengths on the mesophase structure and interlayer spacing, and importantly, whether the zigzag folding-induced formation of a layered structure is retained, despite their unsymmetrical nature.

Local Direction of Optomechanical Stress in Azobenzene Containing Polymers During Surface Relief Grating Formation

AbstractIn this work, it is revealed how the photoinduced deformation of azobenzene containing polymers relates to the local direction of optomechanical stresses generated during irradiation with interference patterns (IPs). It can be substantiated by the modeling approach proposed by Saphiannikova et al., which describes the directional photodeformations in glassy side‐chain azobenzene polymers, and proves that these deformations arise from the reorientation of rigid backbone segments along the light polarization direction. In experiments and modeling, surface relief gratings in pre‐elongated photosensitive colloids of few micrometers length are inscribed using different IPs such as SS, PP, ±45, SP, RL, and LR. The deformation of colloidal particles is studied in situ, whereby the local variation of polymer topography is assigned to the local distribution of the electrical field vector for all IPs. Experimentally observed shapes are reproduced exactly with modeling azopolymer samples as visco‐plastic bodies in the finite element software ANSYS. Orientation approach correctly predicts local variations of the main axis of light‐induced stress in each interference pattern for both initially isotropic and highly oriented materials. With this work, it is suggested that the orientation approach implements a self‐sufficient and convincing mechanism to describe photoinduced deformation in azopolymer films that in principle does not require auxiliary assumptions.

Block copolymer compatibilizer for efficient and stable nonfullerene organic solar cells

High-efficiency nonfullerene organic solar cells with long-term stability is crucial for future commercialization in the field of organic photovoltaics. Herein, we designed and synthesized a block copolymer, namely PM6-b-PTY6, containing both donor PM6 and Y6 segments in the polymer backbone. We then first demonstrated that the use of such block copolymer as a compatibilizer in high-efficiency PM6:Y6 based benchmark nonfullerene solar cells, simultaneously enhancing their power conversion efficiency and long-term stability. Detailed experimental results reveal that the addition of PM6-b-PTY6 into PM6:Y6 blend can effectively optimize carrier dynamic process, enhance donor–acceptor miscibility, and stabilize the blend morphology. Additionally, this strategy shows similar function when applied to other system like D18-Cl:Y6. As a result, enhanced efficiencies of 16.48% and 17.55% for PM6:Y6 and D18-Cl:Y6 solar cell are achieved, respectively. More importantly, the inverted PM6:Y6 devices exhibit improved stability, retaining 0.81 and 0.86 of the initial efficiency after 550 h aging under ambient and thermal stress, respectively. These results indicate that the compatible block copolymer could provide a fresh strategy to design more efficient nonfullerene organic solar cells.

Dependence of charge carrier transport on molecular relaxations in glassy poly(3-hexylthiophene-2,5-diyl) (P3HT)

A positive effect of molecular relaxations and movement of the molecular backbone and chain segments is reported on charge carrier transport in glassy poly(3-hexylthiophene-2,5-diyl). Mechanisms are proposed, above and below the glass transition temperature.

Surface Characteristics of Poly(alkyl methacrylate)s from Molecular Dynamics Simulations Using All-Atom Force Field.

Molecular dynamics (MD) simulations of melt films of poly(alkyl methacrylate)s (PAMAs) with methyl, ethyl, and n-butyl substituents, respectively, have been performed using an all-atom model to investigate their surface and thin film properties. The applied all-atom force fields predict the bulk densities of PAMAs in good agreement with experiments. Moreover, predictions of the surface tensions of PMMA, PEMA, and Pn-BMA melts are in reasonably good agreement with experiments. The density profiles and orientational-order parameters of chain segments show atomic-scale characteristics in the air/polymer interfacial region. In the surface region, the backbone segments of PAMAs form a well-defined layer structure with the chain vectors oriented parallel to the surface, while the ester side-chains strongly segregate to the surface region and show perpendicular orientation to the surface, with the most pronounced surface segregation noted for Pn-BMA. Such surface segregations of chain segments make it difficult to apply a simple relationship between the cohesive energy density and the surface tension of polymers, for example, and should be taken into account in relating the surface/thin film characteristics to the bulk properties of polymers in general.

Probing Polymer Chain Folding in Solution Using Second Harmonic Light Scattering.

Periodically grafted amphiphilic copolymers (PGACs) were earlier shown by us to adopt a zigzag folded conformation in the solid state, which enabled the backbone and pendant segments to segregate and occupy alternate layers in a lamellar structure. The conformational transition from a random coil to a zigzag folded chain in solution is an interesting problem, which is largely unexplored. To examine this, an orthogonally clickable parent polyester was sequentially clicked with two types of poly(ethylene glycol) (PEG) segments: one is a simple PEG and the other is a PEG that carries a dipolar chromophore. These two hydrophilic PEG segments, installed in a periodic and alternating fashion along the hydrocarbon-rich (HC) polyester backbone, ensure that the Janus folded chains are formed upon folding and carry chromophoric dipoles oriented along the same direction, thereby generating a large net dipole. The folding-induced alignment of chromophores in solution was followed using second harmonic light scattering (SHLS), wherein the intensity of the frequency-doubled scattered light (I2ω) is measured. Folding was induced by adding a polar solvent, like methanol, to a chloroform solution of the polymer; methanol desolvates the HC backbone but solubilizes the pendant PEG segments, thus inducing folding. The second harmonic intensity (I2ω) increased initially with methanol concentration and then saturated; in contrast, I2ω remained invariant with the solvent composition in the case of an analogous model chromophore. Furthermore, in a model PGAC carrying chromophore-bearing PEG segments on every repeat unit, I2ω decreased with increasing methanol composition, revealing the formation of a centrosymmetric folded chain, wherein the chromophoric dipoles on either side cancel each other. Thus, this study clearly reveals that the zigzag chain folding of PGACs can be induced by a segment-selective solvent, resulting in the rather elusive directional ordering of chromophoric dipoles in solution.

Local topology and bifurcation hot-spots in proteins with SARS-CoV-2 spike protein as an example.

Novel topological methods are introduced to protein research. The aim is to identify hot-spot sites where a bifurcation can alter the local topology of the protein backbone. Since the shape of a protein is intimately related to its biological function, a substitution that causes a bifurcation should have an enhanced capacity to change the protein’s function. The methodology applies to any protein but it is developed with the SARS-CoV-2 spike protein as a timely example. First, topological criteria are introduced to identify and classify potential bifurcation hot-spot sites along the protein backbone. Then, the expected outcome of asubstitution, if it occurs, is estimated for a general class of hot-spots, using a comparative analysis of the surrounding backbone segments. The analysis combines the statistics of structurally commensurate amino acid fragments in the Protein Data Bank with general stereochemical considerations. It is observed that the notorious D614G substitution of the spike protein is a good example of a bifurcation hot-spot. A number of topologically similar examples are then analyzed in detail, some of them are even better candidates for a bifurcation hot-spot than D614G. The local topology of the more recently observed N501Y substitution is also inspected, and it is found that this site is proximal to a different kind of local topology changing bifurcation.