Oily wastewater discharged by industrial development is an important factor causing water pollution. Membrane separation technology has the advantages of low cost, simple operation, and high efficiency in the treatment of oily wastewater. However, membrane materials are easily eroded by microorganisms during long-term storage or use, thereby resulting in reduced separation efficiency. Herein, a zeolite imidazole skeleton-8@silver nanocluster composite polyacrylonitrile (ZIF-8@AgNCs/PAN) nanofibrous membrane was fabricated by electrospinning and in situ growth technology. The surface chemistry, morphology, and wettability of the composite membranes were characterized. The carboxyl groups on the surface of hydrolyzed PAN nanofibers, which can be complexed with zinc ions (Zn2+), are utilized as growth sites for porous metal organic frameworks (ZIF-8). Meanwhile, AgNCs are loaded into ZIF-8 to achieve stable hybridization of ZIF-8@AgNCs and nanofibers. The loading quantity of ZIF-8@AgNCs, which can dominantly affect the surface roughness and the porosity of the membranes, is regulated by the feeding amount of AgNCs. The ZIF-8@AgNCs/PAN membrane achieves effective oil-water separation with high separation efficiency toward petroleum ether-in-water emulsion (98.6%) and permeability (62 456 ± 1343 Lm-2 h-1 bar-1). Furthermore, the ZIF-8@AgNCs/PAN membrane possesses high antibacterial activity against Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus), which is beneficial for the long-term storage and use of the membrane.

In this study, WE43 magnesium alloy was produced by the powder metallurgy method. Microstructural analyses of the produced samples were carried out using the scanning electron microscopy method. X-ray fluorescence, energy dispersive x-ray (EDS) analysis, and hardness tests were also implemented to investigate the physical and chemical properties of the alloys. The volumetric hardness was measured to be approximately 53 HV. The microstructural analysis and EDS results indicated the presence of Mg24Y5 and Mg41Nd5 phases in the alloys. Reciprocating-type experiments were carried out in dry and corrosive environments to evaluate the wear resistance. Hanks's solution containing 2% g/l glucose was used as the corrosive environment. Gluconic acid resulting from the oxidation of glucose in the Hanks's solution formed a new thin layer on the alloy surface, which was observed in the worn surface images. The formation of the thin film on the alloy surface resulted in an increase in wear resistance by 37%. The results unraveled the potential of the WE43 alloys as implant materials in areas in contact with glucose.

In beam-based ionization methods, the substrate plays an important role on the desorption mechanism of molecules from surfaces. Both the specific orientation that a molecule adopts at a surface and the strength of the molecule-surface interaction can greatly influence desorption processes, which in turn will affect the ion yield and the degree of in-source fragmentation of a molecule. In the beam-based method of secondary ion mass spectrometry (SIMS), in-source fragmentation can be significant and molecule specific due to the hard ionization method of using a primary ion beam for molecule desorption. To investigate the role of the substrate on orientation and in-source fragmentation, we have used atomistic simulations—molecular dynamics in combination with density functional theory calculations—to explore the desorption of a sphingolipid (palmitoylsphingomyelin) from a model surface (gold). We then compare SIMS data from this model system to our modeling findings. Using this approach, we found that the combined adsorption and binding energy of certain bonds associated with the headgroup fragments (C3H8N+, C5H12N+, C5H14NO+, and C5H15PNO4+) was a good predictor for fragment intensities (as indicated by relative ion yields). This is the first example where atomistic simulations have been applied in beam-based ionization of lipids, and it presents a new approach to study biointerfacial lipid ordering effects on SIMS imaging.

Hydrogels are soft hydrated polymer networks that are widely used in research and industry due to their favorable properties and similarity to biological tissues. However, it has long been difficult to create a hydrogel emulating the heterogeneous structure of special tissues, such as cartilage. One potential avenue to develop a structural variation in a hydrogel is the “mold effect,” which has only recently been discovered to be caused by absorbed oxygen within the mold surface interfering with the polymerization. This induces a dilute gradient-density surface layer with altered properties. However, the precise structure of the gradient-surface layer and its contact response have not yet been characterized. Such knowledge would prove useful for designs of composite hydrogels with altered surface characteristics. To fully characterize the hydrogel gradient-surface layer, we created five hydrogel compositions of varying monomer and cross-linker content to encompass variations in the layer. Then, we used particle exclusion microscopy during indentation and creep experiments to probe the contact response of the gradient layer of each composition. These experiments showed that the dilute structure of the gradient layer follows evolving contact behavior allowing poroelastic squeeze-out at miniscule pressures. Stiffer compositions had thinner gradient layers. This knowledge can potentially be used to create hydrogels with a stiff load-bearing bulk with altered surface characteristics tailored for specific tribological applications.

This paper summarizes the early research results on studying proteins and peptides at interfaces using sum frequency generation (SFG) vibrational spectroscopy. SFG studies in the C—H stretching frequency region to examine the protein side-chain behavior and in the amide I frequency region to investigate the orientation and conformation of interfacial peptides/proteins are presented. The early chiral SFG research and SFG isotope labeling studies on interfacial peptides/proteins are also discussed. These early SFG studies demonstrate the feasibility of using SFG to elucidate interfacial molecular structures of peptides and proteins in situ, which built a foundation for later SFG investigations on peptides and proteins at interfaces.

This is the second half of a two-part Tutorial on the basics of the time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis of bio-related samples. Part I of this Tutorial series covers planning for a ToF-SIMS experiment, preparing and shipping samples, and collecting ToF-SIMS data. This Tutorial aims at helping the ToF-SIMS user to process, display, and interpret ToF-SIMS data. ToF-SIMS provides detailed chemical information about surfaces but comes with a steep learning. The purpose of this Tutorial is to provide the reader with a solid foundation in the ToF-SIMS data analysis.

Interactions between molecules in the synovial fluid and the cartilage surface may play a vital role in the formation of adsorbed films that contribute to the low friction of cartilage boundary lubrication. Osteoarthritis (OA) is the most common degenerative joint disease. Previous studies have shown that in OA-diseased joints, hyaluronan (HA) not only breaks down resulting in a much lower molecular weight (MW), but also its concentration is reduced ten times. Here, we have investigated the structural changes of lipid-HA complexes as a function of HA concentration and MW to simulate the physiologically relevant conditions that exist in healthy and diseased joints. Small angle neutron scattering and dynamic light scattering were used to determine the structure of HA-lipid vesicles in bulk solution, while a combination of atomic force microscopy and quartz crystal microbalance was applied to study their assembly on a gold surface. We infer a significant influence of both MW and HA concentrations on the structure of HA-lipid complexes in bulk and assembled on a gold surface. Our results suggest that low MW HA cannot form an amorphous layer on the gold surface, which is expected to negatively impact the mechanical integrity and longevity of the boundary layer and could contribute to the increased wear of the cartilage that has been reported in joints diseased with OA.

Medical devices are becoming more and more significant in our daily life. For implantable medical devices, good biocompatibility is required for further use in vivo. Thus, surface modification of medical devices is really important, which gives a wide application scene for a silane coupling agent. The silane coupling agent is able to form a durable bond between organic and inorganic materials. The dehydration process provides linking sites to achieve condensation of two hydroxyl groups. The forming covalent bond brings excellent mechanical properties among different surfaces. Indeed, the silane coupling agent is a popular component in surface modification. Metals, proteins, and hydrogels are using silane coupling agent to link parts commonly. The mild reaction environment also brings advantages for the spread of the silane coupling agent. In this review, we summarize two main methods of using the silane coupling agent. One is acting as a crosslinker mixed in the whole system, and the other is to provide a bridge between different surfaces. Moreover, we introduce their applications in biomedical devices.

When polymer chains are grafted to solid surfaces at sufficiently high density, they form brushes that can modify the surface properties. In particular, polymer brushes are increasingly being used to reduce friction in water-lubricated systems close to the very low levels found in natural systems, such as synovial joints. New types of polymer brush are continually being developed to improve with lower friction and adhesion, as well as higher load-bearing capacities. To complement experimental studies, molecular simulations are increasingly being used to help to understand how polymer brushes reduce friction. In this paper, we review how molecular simulations of polymer brush friction have progressed from very simple coarse-grained models toward more detailed models that can capture the effects of brush topology and chemistry as well as electrostatic interactions for polyelectrolyte brushes. We pay particular attention to studies that have attempted to match experimental friction data of polymer brush bilayers to results obtained using molecular simulations. We also critically look at the remaining challenges and key limitations to overcome and propose future modifications that could potentially improve agreement with experimental studies, thus enabling molecular simulations to be used predictively to modify the brush structure for optimal friction reduction.

Developing molecular models to capture the complex physicochemical architecture of the bacterial cell wall and to study the interaction with antibacterial molecules is an important aspect of assessing and developing novel antimicrobial molecules. We carried out molecular dynamics simulations using an atomistic model of peptidoglycan to represent the architecture for Gram-positive S. aureus. The model is developed to capture various structural features of the Staphylococcal cell wall, such as the peptide orientation, area per disaccharide, glycan length distribution, cross-linking, and pore size. A comparison of the cell wall density and electrostatic potentials is made with a previously developed cell wall model of Gram-negative bacteria, E. coli, and properties for both single and multilayered structures of the Staphylococcal cell wall are studied. We investigated the interactions of the antimicrobial peptide melittin with peptidoglycan structures. The depth of melittin binding to peptidoglycan is more pronounced in E. coli than in S. aureus, and consequently, melittin has greater contacts with glycan units of E. coli. Contacts of melittin with the amino acids of peptidoglycan are comparable across both the strains, and the D-Ala residues, which are sites for transpeptidation, show enhanced interactions with melittin. A low energetic barrier is observed for translocation of a naturally occurring antimicrobial thymol with the four-layered peptidoglycan model. The molecular model developed for Gram-positive peptidoglycan allows us to compare and contrast the cell wall penetrating properties with Gram-negative strains and assess for the first time binding and translocation of antimicrobial molecules for Gram-positive cell walls.

In this study, casting, extrusion, biocorrosion, and corrosive wear properties of 0.5 wt. % (Zn, Ca, and Nd) element added Mg—3 wt. % Ag alloys were investigated. According to the test results, it was observed that the grain refinement occurred with the effect of Zn and Ca element additions in the as-cast alloys and thus some mechanical properties of the alloys improved. Similarly, the extrusion process provided grain refinement and improved mechanical properties. As a result of in vitro corrosion tests, similar results were also obtained in the as-cast alloys, while this situation became more apparent in the extruded alloys and exhibited more homogeneous corrosion properties. In the corrosive wear tests, the wear rate of the extruded alloys generally showed a decreasing trend. However, both the as-cast and extruded Mg—3 wt. %Ag—0.5 wt. % Ca alloys exhibited the lowest wear rate.

Novel antimicrobials or new treatment strategies are urgently needed to treat Pseudomonas aeruginosa (P. aeruginosa) related infections and especially to address the problem of antibiotic resistance. We propose a novel strategy that combines the human antimicrobial peptide (AMP) LL37 with different antibiotics to find synergistic AMP-antibiotic combinations against P. aeruginosa strains in vitro. Our results showed that LL37 exhibited synergistic inhibitory and bactericidal effects against P. aeruginosa strains PAO1 and PA103 when combined with the antibiotics vancomycin, azithromycin, polymyxin B, and colistin. In addition, LL37 caused strong outer membrane permeabilization, as demonstrated through measurement of an increased uptake of the fluorescent probe N-phenyl-1-naphthylamine. The membrane permeabilization effects appear to explain why it was easier to rescue the effectiveness of the antibiotic toward the bacteria because the outer membrane of P. aeruginosa exhibits barrier function for antibiotics. Furthermore, the change in the zeta potential was measured for P. aeruginosa strains with the addition of LL37. Zeta potentials for P. aeruginosa strains PAO1 and PA103 were −40.9 and −10.9 mV, respectively. With the addition of LL37, negative zeta potentials were gradually neutralized. We found that positively charged LL37 can interact with and neutralize the negatively charged bacterial outer membrane through electrostatic interactions, and the process of neutralization is believed to have contributed to the increase in outer membrane permeability. Finally, to further illustrate the relationship between outer membrane permeabilization and the uptake of antibiotics, we used LL37 to make the outer membrane of P. aeruginosa strains more permeable, and minimum inhibitory concentrations (MICs) for several antibiotics (colistin, gentamicin, polymyxin B, vancomycin, and azithromycin) were measured. The MICs decreased were twofold to fourfold, in general. For example, the MICs of azithromycin and vancomycin decreased more than fourfold when against P. aeruginosa strain PAO1, which were the greatest decrease of any of the antibiotics tested in this experiment. As for PA103, the MIC of polymyxin B2 decreased fourfold, which was the strongest decrease seen for any of the antibiotics tested in this experiment. The increased uptake of antibiotics not only demonstrates the barrier role of the outer membrane but also validates the mechanism of synergistic effects that we have proposed. These results indicate the great potential of an LL37-antibiotic combination strategy and provide possible explanations for the mechanisms behind this synergy.

Osteoarthritis (OA) is a whole joint disease marked by the degradation of the articular cartilage (AC) tissue, chronic inflammation, and bone remodeling. Upon AC’s injury, proinflammatory mediators including interleukin 1β (IL1β) and lipopolysaccharides (LPS) play major roles in the onset and progression of OA. The objective of this study was to mechanistically detect and compare the effects of IL1β and LPS, separately, on the morphological and nanomechanical properties of bovine chondrocytes. Cells were seeded overnight in a full serum medium and the next day divided into three main groups: A negative control (NC) of a reduced serum medium and 10 ng/ml IL1ß or 10 ng/ml LPS-modified media. Cells were induced for 24 h. Nanomechanical properties (elastic modulus and adhesion energy) and roughness were quantified using atomic force microscopy. Nitric oxide, prostaglandin 2 (PGE2), and matrix metalloproteinases 3 (MMP3) contents; viability of cells; and extracellular matrix components were quantified. Our data revealed that viability of the cells was not affected by inflammatory induction and IL1ß induction increased PGE2. Elastic moduli of cells were similar among IL1β and NC while LPS significantly decreased the elasticity compared to NC. IL1ß induction resulted in least cellular roughness while LPS induction resulted in least adhesion energy compared to NC. Our images suggest that IL1ß and LPS inflammation affect cellular morphology with cytoskeleton rearrangements and the presence of stress fibers. Finally, our results suggest that the two investigated inflammatory mediators modulated chondrocytes’ immediate responses to inflammation in variable ways.

Sum frequency generation vibrational spectroscopy (SFG-VS) is an intrinsically surface-selective vibrational spectroscopic technique based on the second-order nonlinear optical process. Since its birth in the 1980s, SFG-VS has been used to solve interfacial structure and dynamics in a variety of research fields including chemistry, physics, materials sciences, biological sciences, environmental sciences, etc. Better understanding of SFG-VS instrumentation is no doubt an essential step to master this sophisticated technique. To address this need, here we will present a Tutorial with respect to the classification, setup layout, construction, operation, and data processing about SFG-VS. We will focus on the steady state Ti:sapphire based broad bandwidth SFG-VS system and use it as an example. We hope this Tutorial is beneficial for newcomers to the SFG-VS field and for people who are interested in using SFG-VS technique in their research.

This article provides a comprehensive theoretical background of electronic sum frequency generation (ESFG), a second-order nonlinear spectroscopy technique. ESFG is utilized to investigate both exposed and buried interfaces, which are challenging to study using conventional spectroscopic methods. By overlapping two incident beams at the interface, ESFG generates a beam at the sum of their frequencies, allowing for the extraction of valuable interfacial molecular information such as molecular orientation and density of states present at interfaces. The unique surface selectivity of ESFG arises from the absence of inversion symmetry at the interfaces. However, detecting weak signals from interfaces requires the ultrafast lasers to generate a sufficiently strong signal. By understanding the theoretical foundations of ESFG presented in this article, readers can gain a solid grasp of the basics of ESFG spectroscopy.

Zwitterionic dendrimer is an effective carrier, which can restore the natural conformation of peptide segments for high bioaffinity by a hydrogen bond-induced conformational constraint approach. However, it is still unknown whether the approach is applicable for the dendrimers with different geometric sizes. Therefore, the characteristics of conjugates made from zwitterionic poly(amidoamine) (PAM) and the arginine-glycine-aspartic acid (RGD) peptide were examined to elucidate the effects of the geometric sizes of the PAM dendrimer on the conformational structure and stability of the peptide. The results show that the RGD fragments had almost the same structure and stability when conjugated with PAM(G3, G4, or G5) dendrimers. However, when conjugated with PAM(G1 or G2) dendrimers, the structural stability of these fragments was found to be much worse. Also, the structure and stability of RGD segments conjugated with PAM(G3, G4, or G5) were not affected when additional EK segments were inserted. Moreover, we observed that RGD fragments conjugated with PAM(G3, G4, or G5) dendrimers were structurally stable and similar when the concentration of NaCl was 0.15 and 0.5M. Furthermore, we show that PAM(G3, G4, or G5)-RGD conjugates bind strongly to integrin αvβ3.

Here, we present a study on agarose thin-film samples that represent a model system for the exopolysaccharide matrix of biofilms. Povidone-iodide (PVP-I) was selected as an antibacterial agent to evaluate our x-ray photoelectron spectroscopy (XPS)-based methodology to trace specific marker elements, here iodine, commonly found in organic matrices of antibiotics. The in-depth distribution of iodine was determined by XPS analyses with variable excitation energies and in combination with argon gas cluster ion beam sputter cycles. On mixed agarose/PVP-I nanometer-thin films, both methods were found to solve the analytical task and deliver independently comparable results. In the mixed agarose/PVP-I thin film, we found the outermost surface layer depleted in iodine, whereas the iodine is homogeneously distributed in the depth region between this outermost surface layer and the interface between the thin film and the substrate. Depletion of iodine from the uppermost surface in the thin-film samples is assumed to be caused by ultrahigh vacuum exposure resulting in a loss of molecular iodine (I2) as reported earlier for other iodine-doped polymers.

In this tutorial review, we discuss how the choice of upconversion pulse shape in broadband vibrational sum-frequency generation (SFG) spectrometer design impacts the chemical or physical insights one can obtain from a set of measurements. A time-domain picture of a vibrational coherence being mapped by a second optical field is described and the implications of how this mapping, or upconversion process, takes place are given in the context of several popular and emerging approaches found in the literature. Emphasis is placed on broadband frequency-domain measurements, where the choice of upconversion pulse enhances or limits the information contained in the SFG spectrum. We conclude with an outline for a flexible approach to SFG upconversion using pulse-shaping methods and a simple guide to design and optimize the associated instrumentation.

Polyethersulfone (PES) membranes are widely used in medical devices, especially intravascular devices such as intravascular bioartificial pancreases. In the current work, the pure PES and PES-pyrolytic carbon (PyC) composite membranes were synthesized and permeability studies were conducted. In addition, the cytocompatibility and hemocompatibility of the pure PES and PES-PyC membranes were investigated. These materials were characterized using peripheral blood mononuclear cell (PBMC) activation, platelet activation, platelet adhesion, ß-cell viability and proliferation, and ß-cell response to hyperglycemia. The results showed that platelet activation decreased from 87.3% to 27.8%. Any alteration in the morphology of sticking platelets was prevented, and the number of attached platelets decreased by modification with PyC. The 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide assay corroborated that PBMC activation was encouraged by the PyC-modified PES membrane surface. It can be concluded that PES-modified membranes show higher hemocompatibility than pure PES membranes. ß-cells cultured on all the three membranes displayed a lower rate of proliferation although the cells on the PES-PyC (0.1 wt. %) membrane indicated a slightly higher viability and proliferation than those on the pure PES and PES-PyC (0.05 wt. %) membranes. It shows that the PES-PyC (0.1 wt. %) membrane possesses superior cytocompatibility over the other membranes.

Magnetic nanoparticle (MNP) induced magnetic hyperthermia has been demonstrated as a promising technique for the treatment of brain tumor. However, lower heating efficiency resulting from low intratumoral accumulation of magnetic nanomaterials is still one of the significant limitations for their thermotherapeutic efficacy. In this study, we have designed a nanobubble structure with MNPs decorated on the shell, which leads to the improvement of magnetocaloric performance under an alternating magnetic field. First, the phospholipid coupled with MNPs as the shell to be self-assembled magnetic nanobubbles (MNBs) was fabricated by a temperature-regulated repeated compression self-assembly approach. Then, the optimal magnetic heating concentration, electric current parameters for producing the magnetic field, and the number of magnetic heating times were investigated for tuning the better magnetoenergy conversion. Finally, the well-defined geometrical orientation of MNPs on the nanobubble structure enhanced hypothermia effect was investigated. The results demonstrate that the MNBs could promote the endocytosis of magnetic nanoparticles by glioma cells, resulting in better therapeutic effect. Therefore, the controlled assembly of MNPs into well-defined bubble structures could serve as a new hyperthermia agent for tumor therapy.