Influences of hydrophilic and hydrophobic substituents on the organization of supramolecular assemblies of porphyrin derivatives formed at the air/water interface

Monolayers and Langmuir–Blodgett (LB) films of several kinds of porphyrin derivatives that have different substituted alkyl chain length, chain numbers and central metals were studied by π-A isotherms, UV–Vis, polarized UV–Vis and fluorescence spectroscopy and low angle X-ray diffractometry (LAXD). The orientation angles of porphyrin rings and alkyl chains were derived from the polarized UV–Vis spectra and LAXD patterns of the monolayers or LB films, respectively. The rings of the freebase porphyrins with different alkyl chain length or number have similar orientation angles in the films due to the same hydrophilic groups on the rings, and those of metal porphyrins have different orientation angles from each other. The orientation of the alkyl chains is related to the special positions of the chains on the rings and the orientation of the rings. The influences of the hydrophilicity of the hydrophilic groups and the alkyl chain number and length on the organization of the supramolecular assemblies of the porphyrin derivatives were discussed.     

Surface wettability of plasma SiOx:H nanocoating-induced endothelial cells' migration and the associated FAK-Rho GTPases signalling pathways

Vascular endothelial cell (EC) adhesion and migration are essential processes in re-endothelialization of implanted biomaterials. There is no clear relationship and mechanism between EC adhesion and migration behaviour on surfaces with varying wettabilities. As model substrates, plasma SiO_x:H nanocoatings with well-controlled surface wettability (with water contact angles in the range of 98.5 ± 2.3° to 26.3 ± 4.0°) were used in this study to investigate the effects of surface wettability on cell adhesion/migration and associated protein expressions in FAK-Rho GTPases signalling pathways. It was found that EC adhesion/migration showed opposite behaviour on the hydrophilic and hydrophobic surfaces (i.e. hydrophobic surfaces promoted EC migration but were anti-adhesions). The number of adherent ECs showed a maximum on hydrophilic surfaces, while cells adhered to hydrophobic surfaces exhibited a tendency for cell migration. The focal adhesion kinase (FAK) inhibitor targeting the Y-397 site of FAK could significantly inhibit cell adhesion/migration, suggesting that EC adhesion and migration on surfaces with different wettabilities involve (p)FAK and its downstream signalling pathways. Western blot results suggested that the FAK-Rho GTPases signalling pathways were correlative to EC migration on hydrophobic plasma SiO_x:H surfaces, but uncertain to hydrophilic surfaces. This work demonstrated that surface wettability could induce cellular behaviours that were associated with different cellular signalling events.     

Recent advances in hydrogel-based anti-infective coatings

Bacterial infections associated with biomedical devices and implants have posed a great challenge to global healthcare systems.These infections are mainly caused by bacterial biofilm formed on the surface of biomaterials,protecting the encapsulated bacteria from conventional antibiotic treatment and attack of the immune system.As the bacterial biofilm is difficult to eradicate,bactericidal and antifouling coatings have emerged as promising strategies to prevent biofilm formation and subsequent infections.Hydrogels with three-dimensional crosslinked hydrophilic networks,tunable mechanical property and large drug-loading capacity are desirable coating materials,which can kill bacteria and/or prevent bacterial adhesion on the surface,inhibiting biofilm formation.Herein,we review recent developments of hydrogels as anti-infective coatings.Particularly,we highlight two chemical approaches(graft-from and graft-to),which have been used to immobilize hydrogels on surfaces,and present advances in the development of bactericidal(contact-killing and antimicrobial-releasing),antifouling(hydrophilic polymer network)and bifunctional hydrogel coatings with both bactericidal and antifouling activities.In addition,the challenges of hydrogel coatings for clinical applications are discussed,and future research directions of anti-infective hydrogel coatings are proposed.     

Microstructural Changes During the Storage of Systems Containing Cetostearyl Alcohol/Polyoxyethylene Alkyl Ether Surfactants

Abstract

Non-ionic emulsifying wax/water ternary systems composed of water, cetostearyl alcohol and non-ionic polyoxyethylene alkyl ether surfactants (R-(OCH₂CH₂)_AOH with polyoxyethylene (POE) chain lengths, A, varying from 10-30 and R = cetostearyl were examined as they aged for several weeks. The technigues employed included Theological (Ferranti-Shirley cone and plate viscometer), microscopical (brightfield and between crossed polars), thermal (thermogravimetry and D.S.C) and ultracentrifuqation.

The rheological properties of the samples were complex. They confirmed, however, that all ternary systems increased in consistency on storage. For each ternary system apparent viscosities (Oapp) increased as the samples aged. In addition, ternary systems prepared with surfactants with long POE chains were generally of a higher consistency than similar ternary systems containing shorter POE chains.

Each ternary system was considered to be composed of crystalline and gel (Lβ), phases dispersed in bulk (free) water. The overall consistency of each system was related to the swelling ability and the relative amounts of gel phase present; this in turn depended on the POE chain length of the surfactant. The structural changes on storage were due to the formation of additional gel phase. This occurred because hydration of POE chains to form gel phase was limited at the high temperature of manufacture. On storage at lower temperature (25*) the increased solubility of the POE chains allowed additional gel phase to form. However, this now occurred relatively slowly because of the crystalline nature of the hydrocarbon chains. Microscopical observations support this theory, for the timescale of observed interaction correlated well with the consistency and ‘free’ water changes on storage.     

Self-assembled monolayers of semi-fluorinated thiols and disulfides with a potentially antibacterial terminal fragment on gold surfaces

Attempts to elaborate the best organized cationic self-assembled monolayers (SAMs) with sulfur derivatives containing potentially bactericidal quaternary ammonium salt moieties have been performed on gold with the final aim to obtain contact-active antibacterial surfaces. Four molecules bearing two hydrocarbon spacers with different lengths between the sulfur atom and the quaternized nitrogen atom, and two different terminal semi-fluorinated alkyl chains have been synthesised and used in view to evaluate their capacity for leading to the highest densities and the highest organization of potentially active molecules on the metal surface. The formation and quality of SAMs characterized by X-ray photoelectron spectroscopy, Internal Reflexion Infra Red Imaging, contact angle and blocking factor measurements depend on the lengths of both the hydrocarbon spacer and terminal perfluorinated chain.     

Bacterial adhesion to phosphorylcholine-based polymers with varying cationic charge and the effect of heparin pre-adsorption

The steady increase in the use of medical implants and the associated rise of medical device infections has fuelled the need for the production of biomaterials with improved biocompatibility. 2-(methacryloyloxyethyl phosphorylcholine) (MPC) based coatings have been used to improve the biocompatibility of a number of different medical devices. Recent studies have investigated the use of a phosphorylcholine modified with cationic charge to encourage specific bio-interaction. Until now the affect of cationic charge incorporation in MPC copolymers on bacterial adhesion has not been investigated. This study attempts to address this by investigating the affect of charge on four different strains of bacteria commonly associated with medical device infections. In addition, the affect of pre-incubating these MPC-copolymers in heparin is also evaluated as this has previously been shown to improve biocompatibility and reduce bacterial adhesion. Bacterial adhesion was assessed by ATP bioluminescence and Scanning Electron Microscopy (SEM). Results suggest that bacterial adhesion generally increased with increasing cationic charge. When samples were however, pre-incubated with heparin a significant reduction in bacterial adhesion to the MPC-based samples was observed. The heparin remained bound and effective at reducing bacterial adhesion to the cationic MPC-based samples even after three weeks incubation in PBS. To conclude, the MPC-based cationic polymer coatings complexed with heparin may provide a promising solution to reduce medical device related infections.     

Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers

Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (? CH₃) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an “active” antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 h, respectively.     

CyclinD1, CDK4, and P21 expression by IEC-6 cells in response to NiTi alloy and polymeric biomaterials

In order to investigate how cells recognize biomaterials, mRNA that was expressed in attached Intestinal epithelial cells (IEC-6) on various suture substrates was evaluated. The expressed cell cycle regulators (cyclin D1, CDK4 and p21) mRNA were then isolated and detected using the real time- polymerase chain reaction (PCR) method. As a result, cyclin D1 gene expression was affected by cell-polymer adhesion and was associated with cell proliferation. In addition, CDK4 gene expression was affected by cell proliferation rather than by cell-biomaterial interaction. The p21 mRNA gene expression was higher in cells on more hydrophilic surfaces than on hydrophobic surfaces. Further, the cyclin D1, CDK4 and p21 gene expression were also influenced by the surface chemistry of suture materials. We concluded that the expression of cyclin D1, CDK4 and p21 mRNA was a powerful method for studying cell-biomaterial interactions or the evaluation of the carcinogenic activity of biomaterials.     

In-vitro study of bacterial adherence to different types of intraocular lenses

The aim of this study was to determine the adherence of Staphylococcus epidermidis to intraocular lenses made of five different biomaterials: polymethylmethacrylate (PMMA), heparinized PMMA, silicone, hydrophilic acrylic, and hydrogel. The extent of bacterial binding was measured by counting. The results were compared using a one-factor variance analysis. Adherence was weakest on hydrogel and strongest on the silicone polymer. Bacterial adherence to the implant surface must therefore depend on the hydrophobicity or hydrophilicity of the biomaterial.     

Interfacial and mechanical properties of epoxy composites containing carbon nanotubes grafted with alkyl chains of different length

Dispersion of the nano-fillers is important in the manufacture of high performance nanocomposites. Dispersion of silane treated CNT/epoxy composites was analyzed for various alkyl chain lengths. Difference in mobility of alkyl chains of different length affects the excluded free volume and repulsive forces. An optimal chain length was observed to impart maximum mechanical and impact properties. Differences in the dispersion of CNT due to alterations in alkyl chain lengths were determined using electrical resistance measurement. Spreading of CNT/epoxy rearranged the CF tow resulting in a change in electrical resistance ratio (CERR) and the differences in alkyl chain length effected CNT spreading. Dispersion and wetting conditions with different alkyl chain lengths resulted in changes in CERR, ILSS and other proprieties. The butyl chain length was optimal of the alkyl chain lengths studied. This is attributed to the butyl chains known good mobility and steric repulsion effects compared to longer alkyl chain lengths.     

Cell adhesion and related phenomena on the surface-modified Au-deposited nerve microelectrode examined by total impedance measurement and cell detachment tests

This study investigated alkanethiolate self-assembled monolayers (SAMs) of varied chain lengths adsorbed upon novel Au-coated microelectrodes, of which the surface properties were quantitatively evaluated by surface characterization and 3T3 fibroblast cell adhesion, total impedance and cell detachment tests. Thin-film SAMs adsorbed upon Au/PI/Si provided a hydrophobic or passive surface with increased water contact angle and initial total impedance. From cell adhesion tests, we can observe that the film formed as a dense-packed spacer resulted in incomplete cell sealing of 3T3 cells upon the surface-modified microelectrode. Thus the decrease in cell coverage rate and in the slope in association with total impedance as a function of cell-surface reaction time can be found. To study the adhesion force of a comparable single cell attached upon varied modified surfaces, a cell detachment test using a triangular probe tip of a well defined cantilever was carried out in medium containing fibroblast cells. Overall, both the peak force and the work required to detach a comparable single cell from the anchoring domain corresponded well to the increased length of alkyl chains adsorbed upon Au/PI/Si. Both measurements on the SAM modified surfaces demonstrated much smaller values than those on the pristine Au/PI/Si surface. These results concluded that a cell-repulsive characteristic was clearly formed on the SAM modified microelectrode surface. The non-adhering properties of surface-modified microelectrodes should provide better sensitivity for neuromuscular stimulation as well as for the recording of infinitesimal neural signals in future applications of neural prostheses.     

Interaction of poly(ethylene glycol)-conjugated phospholipids with supported lipid membranes and their influence on protein adsorption

We studied real-time interaction between poly(ethylene glycol)-conjugated phospholipids (PEG-lipids) and a supported lipid membrane by surface plasmon resonance (SPR) spectroscopy to understand dynamic behaviors of PEG-lipids on living cell membranes. Supported lipid membranes formed on a hydrophobic surface were employed as a model of living cell membrane. We prepared three kinds of PEG-lipids that carried alkyl chains of different lengths for SPR measurements and also performed fluorescence recovery after photobleaching (FRAP) to study the influence of acyl chain length on dynamics on the supported membrane. PEG-lipids were uniformly anchored to lipid membranes with high fluidity without clustering. Incorporation and dissociation rates of PEG-lipids into supported membranes strongly depended on the length of acyl chains; longer acyl chains reduced the incorporation rate and the dissociation rate of PEG-lipid. Furthermore, protein adsorption experiment with bovine serum albumin indicated that PEG modification prevented the adsorption of bovine serum albumin on such supported membrane.     

Surface functionalisation of bacterial cellulose as the route to produce green polylactide nanocomposites with improved properties

The effect of surface functionalisation of bacterial cellulose nanofibrils (BC) and their use as reinforcement for polylactide (PLLA) nanocomposites was investigated. BC was functionalised with various organic acids via an esterification reaction. This rendered the otherwise hydrophilic BC hydrophobic and resulted in better compatibility (interfacial adhesion) between PLLA and BC. A direct wetting method, allowing the determination of the contact angle of polymer droplets on a single BC nanofibre, was developed to quantify the interfacial adhesion between PLLA and functionalised BC. It was found that the contact angle between PLLA droplets and functionalised BC decreased with increasing chain lengths of the organic acids used to hydrophobise BC. A novel method to compound BC with PLLA based on thermally induced phase separation (TIPS) to yield a dry form of pre-extrusion composite was also developed. The mechanical properties of the surface functionalised BC reinforced PLLA nanocomposites showed significant improvements when compared to neat PLLA and BC reinforced PLLA. The thermal degradation and viscoelastic behaviour of the nanocomposites were also improved over neat PLLA.     

Bacterial adhesion to inert thermoplastic surfaces

The adhesion of four bacterial species, two strains of each, to four hydrophobic thermoplastics was observed. Image analysis of adherent cells stained with acridine orange provided a rapid, direct and objective means of measuring adhesion to clear, translucent and opaque surfaces by calculating the percentage area of a microscopic field covered by cells (percentage coverage). There was a highly significant correlation (P>0.05) between percentage coverage value and adherent cell count (obtained manually) for both rods and cocci. Bacterial adhesion to thermoplastics appeared to be strain specific and was not related to polymer composition. Highest percentage coverage values were obtained using hydrophobic bacteria, and lowest using hydrophilic bacteria. There was no relationship between the origin of the organisms (culture collections or isolates from biomaterial-associated infections) and their ability to adhere, after cultivation in brain heart infusion broth. Many factors influence this ability: an awareness of all experimental variables is essential.     

Reduction of 3T3 Fibroblast Adhesion on SS316L by Methyl-Terminated SAMs

Inhibiting the non-specific adhesion of cells and proteins to biomaterials such as stents, catheters and guide wires is an important interfacial issue that needs to be addressed in order to reduce surface-related implant complications. Medical grade stainless steel 316L was used as a model system to address this issue. To alter the interfacial property of the implant, self assembled monolayers of long chain phosphonic acids with -CH(3), -COOH, -OH tail groups were formed on the native oxide surface of medical grade stainless steel 316L. The effect of varying the tail groups on 3T3 fibroblast adhesion was investigated. The methyl terminated phosphonic acid significantly prevented cell adhesion however presentation of hydrophilic tail groups at the interface did not significantly reduce cell adhesion when compared to the control stainless steel 316L.     

Nanogeometry matters: unexpected decrease of capillary adhesion forces with increasing relative humidity

The sticking effect between hydrophilic surfaces occurring at increasing relative humidity (RH) is an everyday phenomenon with uncountable implications. Here experimental evidence is presented for a counterintuitive monotonous decrease of the capillary adhesion forces between hydrophilic surfaces with increasing RH for the whole humidity range. It is shown that this unexpected result is related to the actual shape of the asperity at the nanometer scale: a model based on macroscopic thermodynamics predicts this decrease in the adhesion force for a sharp object ending in an almost flat nanometer-sized apex, in full agreement with experiments. This anomalous decrease is due to the fact that a significant growth of the liquid meniscus formed at the contact region with increasing humidity is hindered for this geometry. These results are relevant in the analysis of the dynamical behavior of nanomenisci. They could also have an outstanding value in technological applications, since the undesirable sticking effect between surfaces occurring at increasing RH could be avoided by controlling the shape of the surface asperities at the nanometric scale.     

An investigation into bacterial attachment to an elastomeric superhydrophobic surface prepared via aerosol assisted deposition

Bacterial attachment is highly dependent on a surfaces microstructure. For example, some rough surfaces provide grooves suitable for bacterial adhesion. Superhydrophobic surfaces with a Cassie-Baxter wetting mechanism are shown to prevent contact between a bacterium and surface attachment points. The surface used in this study is a highly rough thin film made from a silicone elastomer via an aerosol assisted chemical vapour deposition (AACVD) process. The films had water contact angles averaging 165°, a very low slip angle, and were capable of duplicating the Lotus effect. The ability of bacteria (Escherichia coli and Methicillin-resistant Staphylococcus aureus) to adhere to this surface was tested by submersion in a bacterial suspension. The superhydrophobic elastomer surfaces reduced the attachment of the bacteria tested, relative to the control surfaces of plain glass, and flat elastomeric films. The reduction in bacterial adhesion, without the external action of chemicals, gives the elastomer surface deposited with AACVD possible applications in biomedical and catering industries. This progressive study of bacterial adhesion is carried out on an AACVD prepared surface and presents adhesion results from both smooth and highly roughened elastomeric surfaces.     

Physicochemical characterisation and biological evaluation of polyvinylpyrrolidone-iodine engineered polyurethane (Tecoflex<Superscript>®</Superscript>)

Bacterial adhesion and encrustation are the known causes for obstruction or blockage of urethral catheters and ureteral stents, which often hinders their effective use within the urinary tract. In this in vitro study, polyvinylpyrrolidone-iodine (PVP-I) complex modified polyurethane (Tecoflex^®) systems were created by physically entrapping the modifying species during the reversible swelling of the polymer surface region. The presence of the PVP-I molecules on this surfaces were verified by ATR-FTIR, AFM and SEM-EDAX analysis, while wettability of the films was investigated by water contact angle measurements. The modified surfaces were investigated for its suitability as a urinary tract biomaterial by comparing its lubricity and ability to resist bacterial adherence and encrustation with that of base polyurethane. The PVP-I modified polyurethane showed a nanopatterned surface topography and was highly hydrophilic and more lubricious than control polyurethane. Adherence of both the gram positive Staphylococcus aureus (by 86%; **P < 0.01) and gram-negative Pseudomonas aeruginosa (by 80%; *P < 0.05) was significantly reduced on the modified surfaces. The deposition of struvite and hydroxyapatite the major components of urinary tract encrustations were significantly less on PVP-I modified polyurethane as compared to base polyurethane, especially reduction in hydroxyapatite encrustation was particularly marked. These results demonstrated that the PVP-I entrapment process can be applied on polyurethane in order to reduce/lower complications associated with bacterial adhesion and deposition of encrustation on polyurethanes.     

聚乙二醇及其衍生物改性生物医用材料表面的血液相容性

综述了PEG及其衍生物在生物医用材料表面血液相容性改性中的应用,并介绍了对改性后的表面进行表征的常用方法和手段,如反射红外,水接触角,光电子能谱,表面等离子共振,椭圆偏振仪,蛋白质亲和印迹,蛋白质标记等。     

Surface characterization and platelet adhesion studies of aliphatic polyurethanes grafted by fluorocarbon oligomers: effect of fluorocarbon chain length and carboxylic acid group

The surfaces of aliphatic polyurethane films, which were synthesized by 1,6 hexamethylene diisocyanate, poly(tetramethylene glycol) and 1,4 butanediol, were modified by grafting different chain length of fluorocarbon oligomers. The fluorocarbon oligomers on polyurethane surfaces were terminated with trifluorocarbon or carboxylic acid functionality. The alkyl groups were also grafted onto polyurethane surfaces for comparison. The surface characterization and platelet-contacting property were studied using electron spectroscopy for chemical analysis (ESCA), static contact angle analysis and in vitro platelet adhesion experiments. The effects of fluorocarbon oligomers and their terminal functionalities are discussed. The ESCA results demonstrate the fluorocarbon enrichment at the outmost layer in fluorocarbon oligomer grafted polyurethanes. The fluorocarbon content at the surface increases with increasing the chain length of fluorocarbon oligomers. The fluorocarbon oligomer grafted polyurethanes exhibit highly hydrophobic surfaces, while alkyl groups grafted polyurethanes show relatively hydrophobic surfaces compared with the untreated polyurethane. The in vitro platelet adhesion experiments indicated that the fluorocarbon oligomer and carboxylic acid functionality significantly reduced the number and the degree of activation of the adherent platelets.