Fabrication of hydrophobic structures by nanosecond pulse laser

In this paper, a feasibility study of manufacturing anti-bacteria surface on stainless steel 7C27Mo2 used for surgical tools by using nanosecond pulse laser is presented. The effect of laser power on the depth of groove was studied through laser cutting experiment. Micro-pillar arrays of different dimensions and spacing were generated by laser cutting. The wetting characteristics of micro-structured surfaces were assessed by using the static contact angle measurement approach. The measurement results show that the original hydrophilic stainless steel surface can be converted into a hydrophobic surface by using laser structuring as the contact angle can be doubled. This research shows that it is feasible to manufacture hydrophobic microstructures with a laser cutting process

A Convention for Peptoid Monomer Naming

In this document we describe a naming convention for peptoid monomers recently devised at the University of Strathclyde to address the lack of a consistent approach to this topic within the field. Our method is simplified and targeted at assisting those new to the research space, with a view to streamlining communication between those familiar with peptoids and collaborators in adjacent fields. To do this we have linked our convention to pre-existing amino acid nomenclature which is widely taught at undergraduate level in both chemistry and related disciplines

Superhydrophobic structures on 316L stainless steel surfaces machined by nanosecond pulsed laser

In this paper nanosecond laser machining process was developed to improve the hydrophobicity of AISI 316L stainless steel surface. A geometrical model of laser machined Gaussian micro hole, together with constrain conditions, was established for the first time to predict surface contact angle and optimize structure geometries for maximizing its hydrophobicity. The effects of processing laser power and pitch of microstructures on the topography of the machined surface were investigated through laser machining experiment. Subsequently, the water droplet contact angle was measured to evaluate the hydrophobicity of different specimens. Results show that under the laser power of 10 W and 14 W, with the increase of the pitch of microstructures, the contact angle increases until it reaches its peak value then drops gradually. Under the large pitch of microstructure, the contact angle will increase with the increase of the processing laser power. Under the same pitch of microstructure, the contact angle will increase with the increase of ten-point height of surface topography, Sz which is a better parameter than Sa (arithmetical mean height) to characterise hydrophobicity of surface with Gaussian holes. This study shows that large Sz is an essential condition to form the stable and robust Cassie–Baxter state, i.e. a condition to achieve superhydrophobicity. The comparison between the predicted and measured contact angles in experiments shows that the proposed model can accurately predict contact angle and optimize the geometries of the microstructure to achieve maximum hydrophobicity

Crystallization and lamellar nanosheet formation of an aromatic dipeptoid

An aromatic peptoid analogue of the diphenylalanine dipeptide self-assembles in aqueous solution and the first crystal structure was obtained for this class of compound. This reveals molecular packing stabilized by networks of hydrogen bonds. Free-floating nanosheet lamellar structures are observed in solution, which form via cooperative intermolecular interactions driven by π stacking

Chain-end modifications and sequence arrangements of antimicrobial peptoids for mediating activity and nano-assembly

Poly(N-substituted glycine) “peptoids” are an interesting class of peptidomimics that can resist proteolysis and mimic naturally found antimicrobial peptides (AMPs), which exhibit wide spectrum activity against bacteria. This work investigates the possibility of modifying peptoid AMP mimics (AMPMs) with aliphatic lipid “tails” to generate “lipopeptoids” that can assemble into micellar nanostructures, and evaluates their antimicrobial activities. Two families of AMPMs with different distributions of hydrophobic and cationic residues were employed—one with a uniform repeating amphiphilicity, the other with a surfactant-like head-to-tail amphiphilicity. To further evaluate the interplay between self-assembly and activity, the lipopeptoids were variously modified at the AMPM chain ends with a diethylene glycol (EG2) and/or a cationic group (Nlys-Nlys dipeptoid) to adjust amphiphilicity and chain flexibility. Self-assembly was investigated by critical aggregation concentration (CAC) fluorescence assays and dynamic light scattering (DLS). The structure of a key species was also verified by small-angle X-ray scattering (SAXS) and cryo-electron microscopy (cryo-EM). To screen for antibacterial properties, we measured the minimum inhibitory concentrations (MIC) against S. aureus, E. coli, and P. aeruginosa. We found that certain combinations of lipid tail and AMPM sequences exhibit increased antibacterial activity (i.e., decreased MICs). Perhaps counter-intuitively, we were particularly interested in increased MICs in combination with low CACs. Concealing antimicrobial interactions due to packing of AMPMs in nano-assemblies could pave the way to AMPMs that may be “inert” even if unintentionally released and prevent microbes from gaining resistance to the lipopeptoids. Overall, incorporation of EG2 significantly improved lipopeptoids packing while the hydrophobic tail length was found to have a major influence over the MIC. One particular sequence, which we named C15-EG2-(kss)4, exhibited a very low CAC of 34 μM (0.0075 wt.%) and a significantly increased MIC above values for the unmodified AMPM. With the sequence design trends uncovered from this study, future work will focus on discovering more species such as C15-EG2-(kss)4 and on investigating release mechanisms and the potency of the released lipopeptoids

Self-assembly of minimal peptoid sequences

Peptoids are biofunctional N-substituted glycine peptidomimics. Their self-assembly is of fundamental interest because they demonstrate alternatives to conventional peptide structures based on backbone chirality and beta-sheet hydrogen bonding. The search for self-assembling, water-soluble “minimal” sequences, be they peptide or peptidomimic, is a further challenge. Such sequences are highly desired for their compatibility with biomacromolecules and convenient synthesis for broader application. We report the self-assembly of a set of trimeric, water-soluble α-peptoids that exhibit a relatively low critical aggregation concentration (CAC ∼ 0.3 wt %). Cryo-EM and angle-resolved DLS show different sequence-dependent morphologies, namely uniform ca. 6 nm wide nanofibers, sheets, and clusters of globular assemblies. Absorbance and fluorescence spectroscopies indicate unique phenyl environments for π-interactions in the highly ordered nanofibers. Assembly of our peptoids takes place when the sequences are fully ionized, representing a departure from superficially similar amyloid-type hydrogen-bonded peptide nanostructures and expanding the horizons of assembly for sequence-specific bio- and biomimetic macromolecules

Martinoid : the peptoid martini force field

Many exciting innovations have been made in the development of assembling peptoid materials. Typically, these have utilised large oligomeric sequences, though elsewhere the study of peptide self-assembly has yielded numerous examples of assemblers below 6–8 residues in length, evidencing that minimal peptoid assemblers are not only feasible but expected. A productive means of discovering such materials is through the application of in silico screening methods, which often benefit from the use of coarse-grained molecular dynamics (CG-MD) simulations. At the current level of development, CG models for peptoids are insufficient and we have been motivated to develop a Martini forcefield compatible peptoid model. A dual bottom-up and top-down parameterisation approach has been adopted, in keeping with the Martini parameterisation methodology, targeting the reproduction of atomistic MD dynamics and trends in experimentally obtained log D7.4 partition coefficients, respectively. This work has yielded valuable insights into the practicalities of parameterising peptoid monomers. Additionally, we demonstrate that our model can reproduce the experimental observations of two very different peptoid assembly systems, namely peptoid nanosheets and minimal tripeptoid assembly. Further we can simulate the peptoid helix secondary structure relevant for antimicrobial sequences. To be of maximum usefulness to the peptoid research community, we have developed freely available code to generate all requisite simulation files for the application of this model with Gromacs MD software

Constant pH coarse-grained molecular dynamics with stochastic charge neutralization

pH dependence abounds in biochemical systems; however, many simulation methods used to investigate these systems do not consider this property. Using a modified version of the hybrid non-equilibrium molecular dynamics (MD)/Monte Carlo algorithm, we include a stochastic charge neutralization method, which is particularly suited to the MARTINI force field and enables artifact-free Ewald summation methods in electrostatic calculations. We demonstrate the efficacy of this method by reproducing pH-dependent self-assembly and self-organization behavior previously reported in experimental literature. In addition, we have carried out experimental oleic acid titrations where we report the results in a more relevant way for the comparison with computational methods than has previously been done

Surface design for immobilization of an antimicrobial peptide mimic for efficient anti‐biofouling

Microbial surface attachment negatively impacts a wide range of devices from water purification membranes to biomedical implants. Mimics of antimicrobial peptides (AMPs) constituted from poly(N‐substituted glycine) "peptoids" are of great interest as they resist proteolysis and can inhibit a wide spectrum of microbes. We investigate how terminal modification of a peptoid AMP‐mimic and its surface immobilization affect antimicrobial activity. We also demonstrate a convenient surface modification scheme for enabling alkyne‐azide "click" coupling on amino‐functionalized surfaces. Our results verified that the N‐ and C‐terminal peptoid structures are not required for antimicrobial activity. Moreover, our peptoid immobilization density and choice of PEG tether resulted in a "volumetric" spatial separation between AMPs that, compared to past studies, enabled the highest AMP surface activity relative to bacterial attachment. Our analysis suggests the importance of spatial flexibility for membrane activity and that AMP separation may be a controlling parameter for optimizing surface anti‐biofouling

A hybrid laser ablation and chemical etching process for manufacturing nature-inspired anisotropic superhydrophobic structures

The surface with anisotropic superhydrophobicity has great potential applications for drag reduction, drug delivery and microfluidic devices. Observation from natural biological surfaces proved that directional microstructures are indispensable to realize anisotropic superhydrophobicity. However, current lithography-based manufacturing approaches have limited capabilities to scale-up for real world industrial applications. This paper proposes a hybrid laser ablation and chemical etching process for manufacturing ratchet-like microstructures on 316L stainless steel for the first time. It harvests the advantages of both processes. The laser ablation will form specified recast layer and covered by oxide layer on the specimen, and these two layers can be easily removed in the chemical etching process hence to obtain the periodic ratchet-like microstructures. According to the experimental results, the direction of microstructures is same as with the laser beam feed direction. The width and depth of microstructures also can be well-controlled by laser power and pitch. The specimens with pith of 25 μm have contact angle larger than 150°. And the droplet easily rolls off along the laser beam feed direction but is pinned tightly in the opposite direction