Surface Structure Of Polymers Research Articles

Cryo-EM structures of type IV pili complexed with nanobodies reveal immune escape mechanisms

Type IV pili (T4P) are prevalent, polymeric surface structures in pathogenic bacteria, making them ideal targets for effective vaccines. However, bacteria have evolved efficient strategies to evade type IV pili-directed antibody responses. Neisseria meningitidis are prototypical type IV pili-expressing Gram-negative bacteria responsible for life threatening sepsis and meningitis. This species has evolved several genetic strategies to modify the surface of its type IV pili, changing pilin subunit amino acid sequence, nature of glycosylation and phosphoforms, but how these modifications affect antibody binding at the structural level is still unknown. Here, to explore this question, we determine cryo-electron microscopy (cryo-EM) structures of pili of different sequence types with sufficiently high resolution to visualize posttranslational modifications. We then generate nanobodies directed against type IV pili which alter pilus function in vitro and in vivo. Cryo-EM in combination with molecular dynamics simulation of the nanobody-pilus complexes reveals how the different types of pili surface modifications alter nanobody binding. Our findings shed light on the impressive complementarity between the different strategies used by bacteria to avoid antibody binding. Importantly, we also show that structural information can be used to make informed modifications in nanobodies as countermeasures to these immune evasion mechanisms.

Engineering Polymer Interfaces: A Review toward Controlling Triboelectric Surface Charge

AbstractContact electrification and triboelectric charging are areas of intense research. Despite their low ability to accept or donate electrons, polymer insulator based triboelectric nanogenerators have emerged as highly efficient mechanical‐to‐electrical conversion devices. Here, it is reviewed the structure–property–performance of polymer insulators in triboelectric nanogenerators and focus on tools that can be used to directly enhance charge generation, via altering a polymer's mechanical, thermal, chemical, and topographical properties. In addition to the discussion of these fundamental properties, the use of additives to locally manipulate the polymer surface structure is discussed. The link between each property and the underlying charging mechanism is discussed, in the context of both increasing surface charge and predicting the polarity of surface charge, and pathways to engineer triboelectric charging are highlighted. Key questions facing the field surrounding data reporting, the role of water, and synergy between mass, electron, and ion transfer mechanisms are highlighted with aspirational goals of a holistic model for triboelectric charging proposed.

Efficient Surface Structuring of Photomechanical Solid Polymers by Near-Zero Light Absorption

Mechanics enabled by photon absorption generates work from materials and is perhaps one of the most important applications of light-active matter, which mediates an intensity-to-stress transduction and moves in intensity gradients. Photomechanics can be put at work in surface structuring of materials, which has applications in several areas of science and engineering including photonics and biology and medicine. We demonstrate that photosensitive materials can be unexpectedly micro- and nanotextured by single-step irradiation with weakly absorbed low-power red light. We report highly efficient surface structuring induced by interference patterns of two coherent nonresonant red (wavelength of 632.8 nm), less than 5 mW, laser beams operating in the near-zero absorption tail of azo-polymer films with optical densities in the 0.02–0.09 range, i.e., 80 – 95% light transmission. The heights of the observed structures are comparable to those obtained by resonant absorption, a feature that is counterintuitive and thus never reported to date. Low- and high-energy n – π* and π – π* excitations of the azo dye are equally efficient in inducing isomerization and mass motion of polymers. Our work is of central importance to photomechanics, and to surface texturing in particular, since it demonstrates that efficient material motion can be driven by weekly absorbed, i.e., low-energy excitation, low-power red light, in solid films of polymers well below the glass transition temperature, pointing to possible biological and cost-effective industrial applications.

Doping with Niobium Nanoparticles as an Approach to Increase the Power Conversion Efficiency of P3HT:PCBM Polymer Solar Cells.

Metal additive processing in polymer: fullerene bulk heterojunction systems is recognized as a viable way for improving polymer photovoltage performance. In this study, the effect of niobium (Nb) metal nanoparticles at concentrations of 2, 4, 6, and 8 mg/mL on poly(3-hexylthiophene-2,5-diyl) (P3HT)-6,6]-phenyl C61-butyric acid methyl ester (PCBM) blends was analyzed. The effect of Nb volume concentration on polymer crystallinity, optical properties, and surface structure of P3HT and PCBM, as well as the enhancement of the performance of P3HT:PC61BM solar cells, are investigated. Absorption of the P3HT:PC61BM mix is seen to have a high intensity and a red shift at 500 nm. The reduction in PL intensity with increasing Nb doping concentrations indicates an increase in PL quenching, suggesting that the domain size of P3HT or conjugation length increases. With a high Nb concentration, crystallinity, material composition, surface roughness, and phase separation are enhanced. Nb enhances PCBM's solubility in P3HT and decreases the size of amorphous P3HT domains. Based on the J-V characteristics and the optoelectronic study of the thin films, the improvement results from a decreased recombination current, changes in morphology and crystallinity, and an increase in the effective exciton lifespan. At high doping concentrations of Nb nanoparticles, the development of the short-circuit current (JSC) is associated with alterations in the crystalline structure of P3HT. The highest-performing glass/ITO/PEDOT:PSS/P3HT:PCBM:Nb/MoO3/Au structures have short-circuit current densities (JSC) of 16.86 mA/cm2, open-circuit voltages (VOC) of 466 mV, fill factors (FF) of 65.73%, and power conversion efficiency (µ) of 5.16%.

Green Approach for Manufacturing of Polymer Surface Structures with Microcavities Having Robust Chemically Functionalized Inner Surfaces

Green Approach for Manufacturing of Polymer Surface Structures with Microcavities Having Robust Chemically Functionalized Inner Surfaces

Capturing water vapors from atmospheric air using superporous gels

Dehumidification performance of most polymer desiccant materials is unsatisfactory because of the complex adsorption mechanism on polymer surface and non-porous structure. A viable alternative of solid desiccants, especially existing polymer desiccants, for capturing water vapors from moist air is the super-porous gels (SPGs). The presence of interconnected channels of pores in its structure facilitates the transfer of water molecules to the internal structure of SPGs. Therefore, in this research work, we are proposing N-isopropylacrylamide (NIPAM) and acrylamide (AM) based thermoresponsive SPGs as a potential alternative to the existing conventional solid desiccants. To ensure the formation of interconnected capillary channels, the SPGs were synthesized via gas blowing and foaming technique. Surface morphology of the SPGs was studied using scanning electron microscopy (SEM) and the other physio-chemical characteristics were studied using different techniques like fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD) and thermo-gravimetric analysis (TGA). Water vapors adsorption properties of the SPGs were explored via adsorption isotherm and kinetics. The adsorption isotherm was found to be of type-III isotherm with a maximum adsorption capacity of 0.75 gw/gads at 25 °C and 90% relative humidity. Experimental isotherm data correlated well with BET, FHH and GAB isotherm models. Adsorption kinetics suggested that the water vapors diffusion followed intraparticle diffusion and liquid field driving mechanisms collectively. SPGs exhibited very good regeneration and reusability for ten continuous adsorption/desorption cycles. Therefore, the dehumidification efficiency of synthesized SPGs shows that they have potential to replace most of the conventional solid desiccant materials in use.

Plasma-Induced Modifications on High Density Polyethylene and Polyethylene Terephthalate

This work presents comprehensive study of high density polyethylene (HDPE) and polyethylene terephthalate (PET) surface properties after exposed to 1.5, 3, 4.5 and 6 min oxygen (O2) plasma. The polymer surface structure is analyzed by Raman spectroscopy, which revealed surface restructuring modifications. The contact angle of HDPE and PET decreased gradually, and the work of adhesion is improved with O2 plasma. The water contact angle is reduced from 61.6° to 36.3° for HDPE and from 72.4° to 37.5° for PET by increasing plasma time from 1.5 to 6 min. The surface free energy is enhanced from 27.8 mJ m−2 to 69.0 mJ m−2 for HDPE and from 29.8 mJ m−2 to 67.2 mJ m−2 for PET, when the plasma time increased from 0 to 6 min. The polar groups significantly reduced the hydrophobicity of the irradiated films, and consequently the surface wettability is improved. The results showed observed improvement in surface properties of HDPE and PET polymeric films to be use in different applications such as printings, coatings and optoelectronics.

Application of the water-insoluble, temperature-responsive block polymer poly(butyl methacrylate-block-N-isopropylacrylamide) for pluripotent stem cell culture and cell-selective detachment

Induced pluripotent stem (iPS) cells have been widely studied in regenerative medicine, pathology modeling, and drug screening. Stable mass culture of iPS cells is essential for these applications. iPS cells can spontaneously differentiate into other cells during culture, and removal of these differentiated cells is necessary. Herein, a cost-effective culture method suitable for mass culture and a detailed analysis of the selective detachment of iPS cells are presented. A simple method for coating the water-insoluble thermoresponsive polymer poly (butyl methacrylate-block-N-isopropylacrylamide) on commercially available polystyrene dishes was employed. Analysis of the effects of the polymer composition, coating thickness, and surface structure on iPS cell culture/detachment showed that a coating thickness of approximately 10-40nm using a polymer with a high poly (N-isopropylacrylamide) content was suitable for iPS cell detachment. Moreover, an interesting change in surface morphology was observed following temperature variation, thereby affecting laminin adsorption. Second, selective detachment in cocultures of iPS cells and differentiated cells enabled collection of iPS cells with more than 98% purity. Finally, long-term iPS cell culture was conducted using temperature-responsive cell detachment. Overall, long-term maintenance-free culture of iPS cells was possible without manual removal of differentiated cells.

Elucidating molecular mechanisms of two-dimensional chemical reactions

Elucidating molecular mechanisms of two-dimensional chemical reactions

Effects of hydrolysis treatment on the structure and properties of semi‐interpenetrating superabsorbent polymers

AbstractA semi‐interpenetrating polymer network superabsorbent polymer based on sodium lignosulfonate‐graft‐poly(acrylic acid‐acrylamide)/potassium dihydrogen phosphate and polyvinyl alcohol (PVA/SL‐g‐P[AA‐AM]/KDP) was synthesized by using solution polymerization. The PVA/SL‐g‐P(AA‐AM)/KDP was further hydrolyzed in NaOH solution. The structure, thermal stability, and morphologies of samples were examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results of FTIR, TGA, and DSC showed that PVA interpenetration through SL‐g‐P(AA‐AM)/KDP network has occurred, and PVA/SL‐g‐P(AA‐AM)/KDP was successfully alkaline hydrolyzed. From the SEM images, the high porous and loose surface structure of polymers was formed after hydrolysis, which greatly increased the specific surface area. Samples after hydrolysis exhibited higher equilibrium swelling capacity (1963 g/g) compared to the nonhydrolyzed samples (866 g/g). The swelling kinetics of all samples well complied with the pseudo‐second order swelling kinetics model. Simple hydrolysis treatment not only improved the swelling capacity of PVA/SL‐g‐P(AA‐AM)/KDP but also induced an enhancement on its water retention performance, which made it potentially useful as a water retention agent in the revegetation of abandoned mines or slope wasteland.

Probing Biological Molecule Orientation and Polymer Surface Structure at the Polymer/Solution Interface In Situ.

Polymers are widely used for many applications ranging from biomedical materials, marine antifouling coatings, membranes for biomolecule separation, to substrates for enzyme molecules for biosensing. For such applications, it is important to understand molecular interactions between biological molecules and polymer materials in situ in real time. Such understanding provides vital knowledge to manipulate biological molecule-polymer interactions and to optimize polymer surface structures to improve polymer performance. In this research, sum frequency generation (SFG) vibrational spectroscopy was applied to study interactions between peptides (serving as models for biological molecules) and deuterated polystyrene (d8-PS, serving as a model for polymer materials). The peptide conformations/orientations and polymer surface phenyl orientation during the peptide-d8-PS interactions were determined using SFG. It was found that the π-π interaction between the aromatic amino acids on peptides and phenyl groups on d8-PS surface does not play a significant role. Instead, the peptide-d8-PS interactions are mediated by general hydrophobic interactions between the peptides and the polymer surface.

The Combination of Plasma-Processed Air (PPA) and Plasma-Treated Water (PTW) Causes Synergistic Inactivation of Candida albicans SC5314

Microwave-induced plasma was used for the generation of plasma-processed air (PPA) and plasma-treated water (PTW). By this way, the plasma was able to functionalize the compressed air and the used water to antimicrobial effective agents. Their fungicidal effects by single and combined application were investigated on Candida albicans strain SC5314. The monoculture of C. albicans was cultivated on specimens with polymeric surface structures (PE-stripes). The additive as well as the synergistic fungicidal potential of PPA and PTW was investigated by different process windows of plasma exposure time (5–50 s) and sample treatment time with PPA/PTW (1–5 min). For a single PTW or PPA treatment, an increase in the reduction factor with the indicated treatment time was observed (maximum reduction factor of 1.1 and 1.6, respectively). In comparison, the combined application of PTW and then PPA resulted in antagonistic, additive and synergistic effects, depending on the combination. An application of the synergistically acting processes of PTW for cleaning and PPA for drying can be an innovative alternative to the sanitary processes currently used in production plants.

Результати вивчення особливостей поверхневої структури стоматологічних полімерів для знімного протезування методом скануючої мікроскопії після їх обробки різними полірувальними пастами

Результати вивчення особливостей поверхневої структури стоматологічних полімерів для знімного протезування методом скануючої мікроскопії після їх обробки різними полірувальними пастами

High-Performance Materials for 3D Printing in Chemical Synthesis Applications.

3D printing has emerged as an enabling technology for miniaturization. High-precision printing techniques such as stereolithography are capable of printing microreactors and lab-on-a-chip devices for efficient parallelization of biological and biochemical reactions under reduced uptake of reactants. In the world of chemistry, however, up until now, miniaturization has played a minor role. The chemical and thermal stability of regular 3D printing resins is insufficient for sustaining the harsh conditions of chemical reactions. Novel material formulations that produce highly stable 3D-printed chips are highly sought for bringing chemistry up-to-date on the development of miniaturization. In this work, a brief review of recent developments in highly stable materials for 3D printing is given. This work focuses on three highly stable 3D-printable material systems: transparent silicate glasses, ceramics, and fluorinated polymers. It is further demonstrated that 3D printing is also a versatile technique for surface structuring of polymers to enhance their wetting performance. Such micro/nanostructuring is key to selectively wetting surface patterns that are versatile for chemical arrays and droplet synthesis.

Plasma-Treated Air and Water-Assessment of Synergistic Antimicrobial Effects for Sanitation of Food Processing Surfaces and Environment.

The synergistic antimicrobial effects of plasma-processed air (PPA) and plasma-treated water (PTW), which are indirectly generated by a microwave-induced non-atmospheric pressure plasma, were investigated with the aid of proliferation assays. For this purpose, microorganisms (Listeria monocytogenes, Escherichia coli, Pectobacterium carotovorum, sporulated Bacillus atrophaeus) were cultivated as monocultures on specimens with polymeric surface structures. Both the distinct and synergistic antimicrobial potential of PPA and PTW were governed by the plasma-on time (5–50 s) and the treatment time of the specimens with PPA/PTW (1–5 min). In single PTW treatment of the bacteria, an elevation of the reduction factor with increasing treatment time could be observed (e.g., reduction factor of 2.4 to 3.0 for P. carotovorum). In comparison, the combination of PTW and subsequent PPA treatment leads to synergistic effects that are clearly not induced by longer treatment times. These findings have been valid for all bacteria (L. monocytogenes > P. carotovorum = E. coli). Controversially, the effect is reversed for endospores of B. atrophaeus. With pure PPA treatment, a strong inactivation at 50 s plasma-on time is detectable, whereas single PTW treatment shows no effect even with increasing treatment parameters. The use of synergistic effects of PTW for cleaning and PPA for drying shows a clear alternative for currently used sanitation methods in production plants. Highlights: Non-thermal atmospheric pressure microwave plasma source used indirect in two different modes—gaseous and liquid; Measurement of short and long-living nitrite and nitrate in corrosive gas PPA (plasma-processed air) and complex liquid PTW (plasma-treated water); Application of PTW and PPA in single and combined use for biological decontamination of different microorganisms.

Facile one-step photopatterning of hierarchical polymer structures for highly transparent, flexible superhydrophobic films

Superhydrophobic surfaces with mechanical compliance and optical visibility open up new possibilities in practical applications. This work presents a simple, fast, and cost-effective route to fabricate highly flexible and transparent superhydrophobic films with hierarchical surface morphology. Two-tiered polymeric surface structures are readily obtained by a one-step photopatterning approach in conjunction with a roughened sandpaper template. The hierarchical superhydrophobic polymer (HSP) films show excellent wetting properties (static contact angle of >172° and contact angle hysteresis of <3° after Teflon coating), high optical transmittance (> 84% at 550 nm), and enhanced resistance to water drop impact. In addition, the HSP films exhibit high resistance to repeated bending and pressing deformations (5000 cycles), while stably maintaining their superhydrophobicity. The practical utility of the HSP film is successfully demonstrated through self-cleaning, anti-fogging, and water-jet impact tests.

Helicoidal Patterning of Nanorods with Polymer Ligands.

Chiral packing of ligands on the surface of nanoparticles (NPs) is of fundamental and practical importance, as it determines how NPs interact with each other and with the molecular world. Herein, for gold nanorods (NRs) capped with end-grafted nonchiral polymer ligands, we show a new mechanism of chiral surface patterning. Under poor solvency conditions, a smooth polymer layer segregates into helicoidally organized surface-pinned micelles (patches). The helicoidal morphology is dictated by the polymer grafting density and the ratio of the polymer ligand length to nanorod radius. Outside this specific parameter space, a range of polymer surface structures was observed, including random, shish-kebab, and hybrid patches, as well as a smooth polymer layer. We characterize polymer surface morphology by theoretical and experimental state diagrams. The helicoidally organized polymer patches on the NR surface can be used as a template for the helicoidal organization of other NPs, masked synthesis on the NR surface, as well as the exploration of new NP self-assembly modes.

Helicoidal Patterning of Nanorods with Polymer Ligands

AbstractChiral packing of ligands on the surface of nanoparticles (NPs) is of fundamental and practical importance, as it determines how NPs interact with each other and with the molecular world. Herein, for gold nanorods (NRs) capped with end‐grafted nonchiral polymer ligands, we show a new mechanism of chiral surface patterning. Under poor solvency conditions, a smooth polymer layer segregates into helicoidally organized surface‐pinned micelles (patches). The helicoidal morphology is dictated by the polymer grafting density and the ratio of the polymer ligand length to nanorod radius. Outside this specific parameter space, a range of polymer surface structures was observed, including random, shish‐kebab, and hybrid patches, as well as a smooth polymer layer. We characterize polymer surface morphology by theoretical and experimental state diagrams. The helicoidally organized polymer patches on the NR surface can be used as a template for the helicoidal organization of other NPs, masked synthesis on the NR surface, as well as the exploration of new NP self‐assembly modes.

Repeated detection of polystyrene microbeads in the Lower Rhine River

Microplastics are emerging pollutants in water bodies worldwide. The environmental entry areas must be studied to localise their sources and develop preventative and remedial solutions. Rivers are major contributors to the marine microplastics load. Here, we focus on a specific type of plastic microbead (diameter 286–954 μm, predominantly opaque, white–beige) that was repeatedly identified in substantial numbers between kilometres 677 and 944 of the Rhine River, one of Europe's main waterways. Specifically, we aimed (i) to confirm the reported abrupt increase in microbead concentrations between the cities of Leverkusen and Duisburg and (ii) to assess the concentration gradient of these particles along this stretch at higher resolution. Furthermore, we set out (iii) to narrow down the putative entry stretch from 81.3 km, as reported in an earlier study, to less than 20 km according to our research design, and (iv) to identify the chemical composition of the particles and possibly reveal their original purpose. Surface water filtration (mesh: 300 μm, n = 9) at regular intervals along the focal river stretch indicated the concentration of these spherules increased from 0.05 to 8.3 particles m−3 over 20 km. This spot sampling approach was supported by nine suspended solid samples taken between 2014 and 2017, encompassing the river stretch between Leverkusen and Duisburg. Ninety-five percent of microbeads analysed (202/212) were chemically identified as crosslinked polystyrene-divinylbenzene (PS-DVB, 146/212) or polystyrene (PS, 56/212) via Raman or Fourier-transform infrared spectroscopy. Based on interpretation of polymer composition, surface structure, shape, size and colour, the PS(-DVB) microbeads are likely to be used ion-exchange resins, which are commonly applied in water softening and various industrial purification processes. The reported beads contribute considerably to the surface microplastic load of the Rhine River and their potential riverine entry area was geographically narrowed down.

Surface Water as a Mediator and Reporter of Adhesion at Aqueous Interfaces.

Understanding the adsorption of molecules onto surfaces is integral to a wide variety of fields with scientific, engineering, and industrial applications. The surface-adsorbed structure is governed by the nature of the molecule, surface characteristics, and solution environment. There are therefore three critical interactions that govern adhesion: solvent-analyte, substrate-analyte, and substrate-solvent. The last two interactions require a surface-specific probe restricted to a few nanometers or less. This is particularly true of efforts to probe polymer surface structure without being overwhelmed by bulk polymer signal or interfacial water structure in the presence of bulk water. Second-order nonlinear optical techniques are ideal probes of such interactions, as their reporting depth is determined by the polar arrangement of molecules (a break in the macroscopic inversion symmetry) rather than the penetration of the optical fields. This Account begins with an introduction of surface water structure from the perspective of a nonlinear probe. Details about the unique view of the water orientation distribution are discussed and contrasted with information obtained from conventional vibrational techniques. The salient features of water next to model hydrophobic and hydrophilic surfaces are discussed, in preparation for a discussion of solute interactions that follows. We then present three examples using a combination of linear and nonlinear vibrational spectroscopy and molecular dynamics simulations to illustrate how water is both a mediator and a marker of adhesion. The first is a study of amphipathic peptide adhesion onto hydrophobic and hydrophilic surfaces, characterizing the adsorbed structure in relation to the water surrounding the molecule and trapped near the surface. Water is found to be especially important in mediating adhesion to hydrophilic surfaces, where it aids in solvating the peptide as well as facilitating interactions with the surface. In the second example, we look at adhesion of a multicomponent polymer adhesive using surface-bulk heterospectral correlation analysis, in which surface vibrational spectroscopy is combined with bulk infrared absorption to determine interfacial structure development during the evaporation of water. When acrylic acid is added to the polymer, there is a change in orientation of the polymer before an increase in population. This is opposite to what is observed when no additive is present. In our third example, we show how interfacial water provides a unique window into the surface microenvironment during bacterial adhesion, highlighting the role of solution conditions at the surface in cell attachment and biofilm growth. Changes in the nonlinear vibrational response of interfacial water reflect changes occurring in the pH and ionic strength only at the surface, due to the presence of polymeric adhesives secreted by the bacteria. These studies underline the importance of surface water in governing the structure of adhered molecules and in mediating changes in the interfacial environment as a result of adhesion and provide insight into a nanoscale region that is otherwise difficult to query. They also illustrate the importance of combining surface-sensitive and bulk spectroscopic probes with computer modeling to gain a better understanding of the interplay between water and adsorbate structure.