Engineering Structural Janus MXene-nanofibrils Aerogels for Season-Adaptive Radiative Thermal Regulation.

Aerogels have provided a significant platform for passive radiation-enabled thermal regulation, arousing extensive interest due to their capabilities of radiative cooling or heating. However, there still remains challenge of developing functionally integrated aerogels for sustainable thermal regulation in both hot and cold environment. Here, Janus structured MXene-nanofibrils aerogel (JMNA) is rationally designed via a facile and efficient way. The achieved aerogel presents the characteristic of high porosity (≈98.2%), good mechanical strength (tensile stress of ≈2 MPa, compressive stress of ≈115 kPa), and macroscopic shaping property. Based on the asymmetric structure, the JMNA with switchable functional layers can alternatively enable passive radiative heating and cooling in winter and summer, respectively. As a proof of concept, JMNA can function as a switchable thermal-regulated roof to effectively enable the inner house model to maintain >25 °C in winter and <30 °C in hot summer. This design of Janus structured aerogels with compatible and expandable capabilities is promising to widely benefit the low-energy thermal regulation in changeable climate.

Convergent evolution of skin surface microarchitecture and increased skin hydrophobicity in semi-aquatic anole lizards.

Animals that habitually cross the boundary between water and land face specific challenges with respect to locomotion, respiration, insulation, fouling and waterproofing. Many semi-aquatic invertebrates and plants have developed complex surface microstructures with water-repellent properties to overcome these problems, but equivalent adaptations of the skin have not been reported for vertebrates that encounter similar environmental challenges. Here, we document the first evidence of evolutionary convergence of hydrophobic structured skin in a group of semi-aquatic tetrapods. We show that the skin surface of semi-aquatic species of Anolis lizards is characterized by a more elaborate microstructural architecture (i.e. longer spines and spinules) and a lower wettability relative to closely related terrestrial species. In addition, phylogenetic comparative models reveal repeated independent evolution of enhanced skin hydrophobicity associated with the transition to a semi-aquatic lifestyle, providing evidence of adaptation. Our findings invite a new and exciting line of inquiry into the ecological significance, evolutionary origin and developmental basis of hydrophobic skin surfaces in semi-aquatic lizards, which is essential for understanding why and how the observed skin adaptations evolved in some and not other semi-aquatic tetrapod lineages.

Facile Fabrication of Bio- and Dual-Functional Poly(2-oxazoline) Bottle-Brush Brush Surfaces.

Poly(2-oxazoline)s (POx) bottle-brush brushes have excellent biocompatible and lubricious properties, which are promising for the functionalization of surfaces for biomedical devices. Herein, a facile synthesis of POx is reported which is based bottle-brush brushes (BBBs) on solid substrates. Initially, backbone brushes of poly(2-isopropenyl-2-oxazoline) (PIPOx) were fabricated via surface initiated Cu0 plate-mediated controlled radical polymerization (SI-Cu0 CRP). Poly(2-methyl-2-oxazoline) (PMeOx) side chains were subsequently grafted from the PIPOx backbone via living cationic ring opening polymerization (LCROP), which result in ≈100 % increase in brush thickness (from 58 to 110 nm). The resultant BBBs shows tunable thickness up to 300 nm and high grafting density (σ) with 0.42 chains nm-2 . The synthetic procedure of POx BBBs can be further simplified by using SI-Cu0 CRP with POx molecular brush as macromonomer (Mn =536 g mol-1 , PDI=1.10), which results in BBBs surface up to 60 nm with well-defined molecular structure. Both procedures are significantly superior to the state-of-art approaches for the synthesis of POx BBBs, which are promising to design bio-functional surfaces.

Light-Induced Contraction/Expansion of 1D Photoswitchable Metallopolymer Monitored at the Solid-Liquid Interface.

The use of a bottom-up approach to the fabrication of nanopatterned functional surfaces, which are capable to respond to external stimuli, is of great current interest. Herein, the preparation of light-responsive, linear supramolecular metallopolymers constituted by the ideally infinite repetition of a ditopic ligand bearing an azoaryl moiety and Co(II) coordination nodes is described. The supramolecular polymerization process is followed by optical spectroscopy in dimethylformamide solution. Noteworthy, a submolecularly resolved scanning tunneling microscopy (STM) study of the in situ reversible trans-to-cis photoisomerization of a photoswitchable metallopolymer that self-assembles into 2D crystalline patterns onto a highly oriented pyrolytic graphite surface is achieved for the first time. The STM analysis of the nanopatterned surfaces is corroborated by modeling the physisorbed species onto a graphene slab before and after irradiation by means of density functional theory calculation. Significantly, switching of the monolayers consisting of supramolecular Co(II) metallopolymer bearing trans-azoaryl units to a novel pattern based on cis isomers can be triggered by UV light and reversed back to the trans conformer by using visible light, thereby restoring the trans-based supramolecular 2D packing. These findings represent a step forward toward the design and preparation of photoresponsive "smart" surfaces organized with an atomic precision.

Modulation of Immune Response Using Engineered Nanoparticle Surfaces.

Nanoparticles (NPs) coated with a monolayer of ligands can be recognized by different components of the immune system, opening new doors for the modulation of immunological responses. By the use of different physical or chemical properties at the NP surface (such as charge, functional groups, and ligand density), NPs can be designed to have distinct cellular uptake, cytokine secretion, and immunogenicity, factors that influence the distribution and clearance of these particles. Understanding these immunological responses is critical for the development of new NP-based carriers for the delivery of therapeutic molecules, and as such several studies have been performed to understand the relationships between immune responses and NP surface functionality. In this review, we will discuss recent reports of these structure-activity relationships, and explore how these motifs can be controlled to elicit therapeutically useful immune responses.

Functionalization of metallic glasses through hierarchical patterning.

Surface engineering over multiple length scales is critical for electronics, photonics, and enabling multifunctionality in synthetic materials. Here, we demonstrate a sequential embossing technique for building multi-tier patterns in metals by controlling the size-dependent thermoplastic forming of metallic glasses. Sub-100 nm to millimeter sized features are sculpted sequentially to allow an exquisite control of surface properties. The process can be integrated with net-shaping to transfer functional patterns on three-dimensional metal parts.

Self-oscillating polymer brushes.

An autonomous functional surface has been designed by using self-oscillating polymers that convert the chemical energy of the Belousov-Zhabotinsky reaction into conformational changes of the polymer chains (see picture: red: hydrophobic/collapsed, green: hydrophilic/extended). Self-oscillating polymer brushes were grafted onto the inner surface of a glass capillary, and autonomous propagation of a chemical wave was observed.

Bridging the Gap-Thermofluidic Designs for Precision Bioelectronics.

Bioelectronics, the merging of biology and electronics, can monitor and modulate biological behaviors across length and time scales with unprecedented capability. Current bioelectronics research largely focuses on devices' mechanical properties and electronic designs. However, the thermofluidic control is often overlooked, which is noteworthy given the discipline's importance in almost all bioelectronics processes. It is believed that integrating thermofluidic designs into bioelectronics is essential to align device precision with the complexity of biofluids and biological structures. This perspective serves as a mini roadmap for researchers in both fields to introduce key principles, applications, and challenges in both bioelectronics and thermofluids domains. Important interdisciplinary opportunities for the development of future healthcare devices and precise bioelectronics will also be discussed.

Post-Polymerization Modification of Fluoropolymers via UV Irradiation in the Presence of a Photoacid Generator.

Fluorinated polymers have unique wettability and protein adsorption properties. The site-specific alteration of these properties could expand their application to different research areas. In this work, a fluorinated homopolymer and two of its copolymers with 4-vinylbenzyl glycidyl ether (VBGE) are synthesized by free radical polymerization. The produced polymers are then used to develop resist formulations by the addition of a photoacid generator. Films of these formulations are exposed to ultraviolet radiation through a binary mask and heated to create the pattern. It is found that the water contact angle values of the exposed films areas are reduced compared to those of the unexposed ones, with the exception of pentafluorophenyl methacrylate (PFMA) homopolymer film. This is attributed to the reaction of the epoxy groups creating x-links and producing hydroxyl groups and the cleavage of the pentafluorophenyl group from the ester group leading to carboxylic acid groups. Both modifications on the exposed areas are verified by FTIR spectroscopy and ToF-SIMS analysis. In addition, the biomolecules adsorption ability of the exposed area is increasing 10-15 times compared to the unexposed one for the PFMA homopolymer and the PFMA/VBGE 1:1 copolymer. Thus, the proposed polymers and patterning procedure could find application to spatially directed immobilization of biomolecules and/or cells onto a surface for both biosensing and tissue engineering purposes.

Nanohydroxyapatite-Coated Titanium Surface Increases Vascular Endothelial Cells Distinct Signaling Responding to High Glucose Concentration.

AIM: The success of dental implants depends on osseointegration can be compromised by well-known related adverse biological processes, such as infection and diabetes. Previously, nanohydroxyapatite-coated titanium surfaces (nHA_DAE) have been shown to contain properties that promote osteogenesis by enhancing osteoblast differentiation. In addition, it was hypothesized to drive angiogenesis in high-glucose microenvironments, mimicking diabetes mellitus (DM). On the other hand, the null hypothesis would be confirmed if no effect was observed in endothelial cells (ECs). MATERIALS AND METHODS: Titanium discs presenting the differential surfaces were previously incubated in an FBS-free cell culture medium for up to 24 h, which was, thereafter, supplemented with 30.5 mM of glucose to expose human umbilical vein endothelial cells (HUVECs, ECs) for 72 h. They were then harvested, and the sample was processed to provide molecular activity of specific genes related to EC survival and activity by using qPCR, and the conditioned medium by ECs was used to evaluate the activity of matrix metalloproteinases (MMPs). RESULTS: Our data guaranteed better performance of this nanotechnology-involved titanium surface to this end once the adhesion and survival characteristics were ameliorated by promoting a higher involvement of ß1-Integrin (~1.5-fold changes), Focal Adhesion Kinases (FAK; ~1.5-fold changes) and SRC (~2-fold changes) genes. This signaling pathway culminated with the cofilin involvement (~1.5-fold changes), which guaranteed cytoskeleton rearrangement. Furthermore, nHA_DAE triggered signaling that was able to drive the proliferation of endothelial cells once the cyclin-dependent kinase gene was higher in response to it, while the P15 gene was significantly down-regulated with an impact on the statement of angiogenesis. CONCLUSIONS: Altogether, our data show that a nanohydroxyapatite-coated titanium surface ameliorates the EC performance in a high-glucose model in vitro, suggesting its potential application in DM patients.

Process Optimization for Manufacturing Functional Nanosurfaces by Roll-to-Roll Nanoimprint Lithography.

Roll-to-roll nanoimprint lithography (RTR-NIL) is a low-cost and continuous fabrication process for large-area functional films. However, the partial ultraviolet (UV) resin filling obstructs the ongoing production process. This study incorporates UV resin filling process into the nanopillars and nanopores by using RTR-NIL. A multiphase numerical model with a sliding mesh method is proposed in this study to show the actual phenomena of imprint mold rotation and feeding of UV resin on the polyethylene terephthalate (PET) substrate. The implementation of UV resin filling under environmental conditions was performed by utilizing the open-channel (OC) boundary conditions. The numerical model was solved by using the explicit volume of fluid (VOF) scheme to compute the filling on each node of the computational domain. The effects of different processing parameters were investigated through the proposed numerical model such as imprinting speed (IS), contact angles (CAs), viscosity, initial thickness of the PET, and supporting roll diameter. A good agreement was found between numerical simulations and experimental results. The proposed numerical model gives better insights of the filling process for the mass production of functional surfaces with nanopillars and nanopores patterns for different applications on an industrial scale.

Bioinspired functional SLIPSs and wettability gradient surfaces and their synergistic cooperation and opportunities for enhanced condensate and fluid transport.

Bioinspired smart functional surfaces have received increasing attention in recent years owed to their tunable wettability and enhanced droplet transport suggesting them as excellent candidates for industrial and nanotechnology-related applications. More specifically, bioinspired slippery lubricant infused porous surfaces (SLIPSs) have been proposed for their low adhesion enabling continuous dropwise condensation (DWC) even of low-surface tension fluids. In addition, functional surfaces with chemical and/or structural wettability gradients have also been exploited empowering spontaneous droplet transport in a controlled manner. Current research has focused on the better understanding of the mechanisms and intimate interactions taking place between liquid droplets and functional surfaces or on the forces imposed by differences in surface wettability and/or by Laplace pressure owed to chemical or structural gradients. Nonetheless, less attention has been paid to the synergistic cooperation of efficiently driving droplet transport via chemical and/or structural patterns/gradients on a low surface energy/adhesion background imposed by SLIPSs, with the consequent promising potential for microfluidics and condensation heat transfer applications amongst others. This review provides a detailed and timely overview and summary on recent advances and developments on bioinspired SLIPSs and on wettability gradient surfaces with focus on their synergistic cooperation for condensation and fluid transport related applications. Firstly, the fundamental theory and mechanisms governing complex droplet transport on homogeneous, on wettability gradient surfaces and on inclined SLIPSs are introduced. Secondly, recent advances on the fabrication and characterization of SLIPSs and functional surfaces are presented. Then, the condensation performance on such functional surfaces comprising chemical or structural wettability gradients is reviewed and their applications on condensation heat transfer are summarized. Last a summary outlook highlighting the opportunities and challenges on the synergistic cooperation of SLIPSs and wettability gradient surfaces for heat transfer as well as future perspective in modern applications are presented.

Strategies for Surface Immobilization of Whole Bacteriophages: A Review.

Bacteriophage immobilization is a key unit operation in emerging biotechnologies, enabling new possibilities for biodetection of pathogenic microbes at low concentration, production of materials with novel antimicrobial properties, and fundamental research on bacteriophages themselves. Wild type bacteriophages exhibit extreme binding specificity for a single species, and often for a particular subspecies, of bacteria. Since their specificity originates in epitope recognition by capsid proteins, which can be altered by chemical or genetic modification, their binding specificity may also be redirected toward arbitrary substrates and/or a variety of analytes in addition to bacteria. The immobilization of bacteriophages on planar and particulate substrates is thus an area of active and increasing scientific interest. This review assembles the knowledge gained so far in the immobilization of whole phage particles, summarizing the main chemistries, and presenting the current state-of-the-art both for an audience well-versed in bioconjugation methods as well as for those who are new to the field.

Dropwise condensation: From fundamentals of wetting, nucleation, and droplet mobility to performance improvement by advanced functional surfaces.

As a ubiquitous vapor-liquid phase-change process, dropwise condensation has attracted tremendous research attention owing to its remarkable efficiency of energy transfer and transformative industrial potential. In recent years, advanced functional surfaces, profiting from great progress in modifying micro/nanoscale features and surface chemistry on surfaces, have led to exciting advances in both heat transfer enhancement and fundamental understanding of dropwise condensation. In this review, we discuss the development of some key components for achieving performance improvement of dropwise condensation, including surface wettability, nucleation, droplet mobility, and growth, and discuss how they can be elaborately controlled as desired using surface design. We also present an overview of dropwise condensation heat transfer enhancement on advanced functional surfaces along with the underlying mechanisms, such as jumping condensation on nanostructured superhydrophobic surfaces, and new condensation characteristics (e.g., Laplace pressure-driven droplet motion, hierarchical condensation, and sucking flow condensation) on hierarchically structured surfaces. Finally, the durability, cost, and scalability of specific functional surfaces are focused on for future industrial applications. The existing challenges, alternative strategies, as well as future perspectives, are essential in the fundamental and applied aspects for the practical implementation of dropwise condensation.

Impact of surface topography on the bacterial attachment to micro- and nano-patterned polymer films.

The development of antimicrobial surfaces has become a high priority in recent times. There are two ongoing worldwide health crises: the COVID-19 pandemic provoked by the SARS-CoV-2 virus and the antibiotic-resistant diseases provoked by bacteria resistant to antibiotic-based treatments. The need for antimicrobial surfaces against bacteria and virus is a common factor to both crises. Most extended strategies to prevent bacterial associated infections rely on chemical based-approaches based on surface coatings or biocide encapsulated agents that release chemical agents. A critical limitation of these chemistry-based strategies is their limited effectiveness in time while grows the concerns about the long-term toxicity on human beings and environment pollution. An alternative strategy to prevent bacterial attachment consists in the introduction of physical modification to the surface. Pursuing this chemistry-independent strategy, we present a fabrication process of surface topographies [one-level (micro, nano) and hierarchical (micro+nano) structures] in polypropylene (PP) substrates and discuss how wettability, topography and patterns size influence on its antibacterial properties. Using nanoimprint lithography as patterning technique, we report as best results 82 and 86% reduction in the bacterial attachment of E. coli and S. aureus for hierarchically patterned samples compared to unpatterned reference surfaces. Furthermore, we benchmark the mechanical properties of the patterned PP surfaces against commercially available antimicrobial films and provide evidence for the patterned PP films to be suitable candidates for use as antibacterial functional surfaces in a hospital environment.

Effective Separation for New Therapeutic Modalities Utilizing Temperature-responsive Chromatography.

In recent years, drug discovery and therapeutics trends have shifted from a focus on small-molecule compounds to biopharmaceuticals, genes, cell therapy, and regenerative medicine. Therefore, new approaches and technologies must be developed to respond to these changes in medical care. To achieve this, we applied a temperature-responsive separation system to purify a variety of proteins and cells. We developed a temperature-responsive chromatography technique based on a poly(N-isopropylacrylamide) (PNIPAAm)-grafted stationary phase. This method may be applied to various types of protein and cell separation applications by optimizing the properties of the modified polymers used in this system. Therefore, the developed temperature-responsive HPLC columns and temperature-responsive solid-phase extraction (TR-SPE) columns can be an effective separation tool for new therapeutic modalities such as monoclonal antibodies, nucleic acid drugs, and cells.

Multifunctional, Low Friction, Antimicrobial Approach for Biomaterial Surface Enhancement.

Poly(vinyl chloride) (PVC) biomaterials perform a host of life-saving and life-enhancing roles when employed as medical devices within the body. High frictional forces between the device surface and interfacing tissue can, however, lead to a host of complications including tissue damage, inflammation, pain, and infection. We herein describe a versatile surface modification method using multifunctional hydrogel formulations to increase lubricity and prevent common device-related complications. In a clinically relevant model of the urinary tract, simulating the mechanical and biological environments encountered in vivo, coated candidate catheter surfaces demonstrated significantly lower frictional resistance than uncoated PVC, with reductions in coefficient of friction values of more than 300-fold due to hydration of the surface-localized polymer network. Furthermore, this significant lubrication capacity was retained following hydration periods of up to 28 days in artificial urine at pH 6 and pH 9, representing the pH of physiologically normal and infected urine, respectively, and during 200 repeated cycles of applied frictional force. Importantly, the modified surfaces also displayed excellent antibacterial activity, which could be facilely tuned to achieve reductions of 99.8% in adherence of common hospital-acquired pathogens, Staphylococcus aureus and Proteus mirabilis, relative to their uncoated counterparts through incorporation of chlorhexidine in the coating matrix as a model antiseptic. The remarkable, and pH-independent, tribological performance of these lubricious, antibacterial, and highly durable surfaces offers exciting promise for use of this PVC functionalization approach in facilitating smooth and atraumatic insertion and removal of a wide range of medical implants, ultimately maintaining user health and dignity.

Controllable antibacterial and bacterially anti-adhesive surface fabricated by a bio-inspired beetle-like macromolecule.

Drug resistance to bacteria becomes an emerging intractable problem, therefore, developing novel antibacterial agents has become urgently needed. Herein, a bio-inspired design strategy was adopted to synthesize a series of beetle-like macromolecule of multiple quaternary ammonium salts (QASs), which was designed with different cationic charge densities and numbers of hexadecane chains by adjusting their different quaternization degree (QD). It was found that the fabricated fabric surface with them exhibited controllable and outstanding antibacterial and bacterially anti-adhesive properties. More importantly, the antibacterial efficiency was demonstrated to be enhanced with the increasing of QD, and related to the zeta potential, and surface tension. Additionally, the proposed bacterially anti-adhesive model of action revealed the "resisting effect" of hydration layer which greatly resisted the adhesion of bacteria.

One-Step Eco-Friendly Superhydrophobic Coating Method Using Polydimethylsiloxane and Ammonium Bicarbonate.

Superhydrophobic surfaces offer numerous advantages and have become popular in a wide range of fields. Although many approaches for the modification of surface wettability have been developed, the practical application of superhydrophobic surfaces has been limited by the need for toxic materials and specialized equipment. Herein, a one-step coating method is developed for the fabrication of a superhydrophobic surface to eliminate these limitations. This environmentally friendly coating process uses only two reagents, namely, polydimethylsiloxane and ammonium bicarbonate, to minimize the inconvenience and costs associated with the disposal of used toxic materials. The superhydrophobic surface exhibits excellent durability, and the method is applicable to a variety of target surface shapes, including three-dimensional and complex structures. Besides, a wettability patterned surface and a functional filter for oil/water separation can be fabricated using this method. The numerous advantages of this approach demonstrate great practical application potential of these superhydrophobic surfaces.

Hydrogel Functionalized Polyester Fabrics by UV-Induced Photopolymerization.

We address a strategy to graft hydrogels onto polyethylene terephthalate (PET) fabrics using different acrylate-based monomers. The hydrogel-modified fabrics were prepared by a two-step modification. To this end, double functional groups were firstly introduced onto the PET surface via an aminolysis reaction involving allylamine. The final grafted polymer networks were then obtained after UV-induced radical photopolymerization by varying acrylate monomer types in the presence of a cross-linker. After characterization, the resulting hydrogels showed different morphologies and abrasion resistance performances depending on their chemical nature. UV-photopolymerization is a fast and low-cost method to achieve technical fabrics with specific desired properties.