Drastically lowered protein adsorption on microbicidal hydrophobic/hydrophilic polyelectrolyte multilayers

Polyelectrolyte multilayer films assembled from a hydrophobic N-alkylated polyethylenimine and a hydrophilic polyacrylate were discovered to exhibit strong antifouling, as well as antimicrobial, activities. Surfaces coated with these layer-by-layer (LbL) films, which range from 6 to 10 bilayers (up to 45 nm in thickness), adsorbed up to 20 times less protein from blood plasma than the uncoated controls. The dependence of the antifouling activity on the nature of the polycation, as well as on assembly conditions and the number of layers in the LbL films, was investigated. Changing the hydrophobicity of the polycation altered the surface composition and the resistance to protein adsorption of the LbL films. Importantly, this resistance was greater for coated surfaces with the polyanion on top; for these films, the average zeta potential pointed to a near neutral surface charge, thus, presumably minimizing their electrostatic interactions with the protein. The film surface exhibited a large contact angle hysteresis, indicating a heterogeneous topology likely due to the existence of hydrophobic-hydrophilic regions on the surface. Scanning electron micrographs of the film surface revealed the existence of nanoscale domains. We hypothesize that the existence of hydrophobic/hydrophilic nanodomains, as well as surface charge neutrality, contributes to the LbL film's resistance to protein adsorption.     

Antibacterial activity of plastics coated with silver-doped organic-inorganic hybrid coatings prepared by sol-gel processes

Silver-doped organic-inorganic hybrid coatings were prepared starting from tetraethoxysilane- and triethoxysilane-terminated poly(ethylene glycol)-block-polyethylene by the sol-gel process. They were applied as a thin layer (0.6-1.1 microm) to polyethylene (PE) and poly(vinyl chloride) (PVC) films and the antibacterial activity of the coated films was tested against Gram-negative (Escherichia coli ATCC 25922) and Gram-positive (Staphylococcus aureus ATCC 6538) bacteria. The effect of several factors (such as organic-inorganic ratio, type of catalyst, time of post-curing, silver ion concentration, etc.) was investigated. Measurements at different contact times showed a rapid decrease of the viable count for both tested strains. The highest antibacterial activity [more than 6 log reduction within 6 h starting from 106 colony-forming units (cfu) mL-1] was obtained for samples with an organic-inorganic weight ratio of 80:20 and 5 wt % silver salt with respect to the coating. For the coatings prepared by an acid-catalyzed process, a high level of permanence of the antibacterial activity of the coated films was demonstrated by repeatedly washing the samples in warm water or by immersion in physiological saline solution at 37 degrees C for 3 days. The release of silver ions per square meter of coating is very similar to that previously observed for polyamides filled with metallic silver nanoparticles; however, when compared on the basis of Ag content, the concentration of silver ions released from the coating is much higher than that released from 1 mm thick specimens of polyamide (PA) filled with silver nanoparticles. Transparency and good adhesion of the coating to PE and PVC plastic substrates without any previous surface treatment are further interesting features.     

Bacteriological and chemical changes occurring in Bunker-stored silage covered with biodegradable coating

AIMS: To evaluate the efficacy of a biodegradable silage coating for the ability to protect timothy (Phleum pratensa) type silage against spoilage and its quality under natural conditions. METHODS AND RESULTS: Triplicate mini-silos of silage were prepared for three treatments (1: uncoated; 2: coated with biodegradable coating and 3: sealed with plastic), two types of storage (unprotected or protected from rain) and 10 sampling times (0, 7, 14, 21, 28, 35, 42, 56, 63 and 70 days postensiling). Triplicate mini-silos were opened at each sampling time for microbiological (total aerobic bacteria, lactic acid bacteria, moulds and yeasts) and biochemical analyses [pH, dry matter (DM), water-soluble sugars (WSC), lactic (LA), acetic, propionic and butyric acids content]. The study showed that at day 70, counts of moulds and yeasts in silages protected against rain and coated with biodegradable coating were 5.98 log CFU g(-1) when compared with 5.92 and 3.62 log CFU g(-1) in samples from plastic-sealed silage and uncoated silage, respectively. The pH was low and stable pH (4.34) when compared with uncoated (7.17) and plastic sealed (8.34) silages (P < or = 0.05). A DM, WSC and LA content of 421.7, 13.4 and 20.9 g kg(-1) was, respectively, observed. For silage stored outdoors, a level of moulds and yeasts of 3.77 log CFU g(-1) of silage was also observed in silages coated with biodegradable coating after 28 days of storage. A stable pH showing a mean value of 4 was also observed. The pH, DM, WSC and LA content were, respectively, 4.18, 341.1, 13.34 and 31.8 g kg(-1) in these samples. After 70 days of storage, the level of moulds and yeasts on silage sealed with biodegradable coating was 7.73 log CFU g(-1). A DM, WSC and LA content of 291.9, 5.56 and 10.0 g kg(-1) was, respectively, observed. CONCLUSIONS: When compared with uncoated silage, the application of biodegradable coating can preserve the quality of silage for up to a month when exposed to rain and up to 70 days when protected from rain. SIGNIFICANCE AND IMPACT OF THE STUDY: Results emphasize the possibility of the use of a biodegradable coating as an alternative to plastic film for sealing horizontal bunker silos.     

Making thin polymeric materials, including fabrics, microbicidal and also water-repellent

A procedure is developed and validated for making a non-functionalized polyolefin fabric/film highly bactericidal and fungicidal which involves a free-radical grafting of maleic anhydride, followed by an attachment of polyethylenimine (PEI) and its subsequent N-alkylation. Separately, cotton fabric coated with a micron layer of a hydrophobic polymer using hot-filament chemical vapor deposition is rendered markedly hydrophobic; if this coating is preceded by immobilization of N-alkyl-PEI, the fabric becomes both water-repellent and bactericidal.     

Probing soft polymeric coatings of a capillary by atomic force microscopy

Atomic force microscopy (AFM) has been used to probe the surface of a capillary after coating with “soft” polymers, notably polyacrylamides. The aim was the investigation of the efficiency of coverage of the silica surface, so as to reduce or eliminate the electroosmotic flow (EOF), particularly noxious in the separation of macromolecules. The quality of such coating is strongly dependent on two variables: temperature and pH. In the first case, progressively higher temperatures produce open silica patches, where no polymer seems to be bound. The transition from coated to largely uncoated surfaces occurs at 50°C. Also the pH of the polymerizing solution strongly affects the coating efficiency. Since in all coating procedures the monomer solution is not buffered, addition of accelerator (TEMED, N,N,N′N′-tetramethylethylendiamine) induces polymer growth at pH 10–11. These pH values generate hydrolysis of the siloxane bridge anchoring the bifunctional agent (Bind Silane, onto which the polymer chain should grow) to the wall. Thus, coating and de-coating occur simultaneously. Low temperatures during polymer growth (typically 10°C) and buffered solutions (pH 7, titrated after TEMED addition) ensure a most efficient and thorough coating, with virtual elimination of EOF: well coated capillaries exhibit residual EOF values, at pH 10, of the order of 10⁻⁷ cm² V⁻¹ s⁻¹ vs. a standard value for uncoated capillaries of the order of 10⁻⁴ cm² V⁻¹ s⁻¹. The AFM data have been fully confirmed by direct measurement of EOF in coated and uncoated capillaries under an electric field.     

Flame retardant finishing of cotton fabric based on synergistic compounds containing boron and nitrogen

Boric acid and compound containing nitrogen, 2,4,6-tri[(2-hydroxy-3-trimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-HTAC) were used to finish cotton fabric. The flame retardant properties of the finished cotton fabrics and the synergetic effects of boron and nitrogen elements were investigated and evaluated by limited oxygen index (LOI) method. The mechanism of cross-linking reaction among cotton fiber, Tri-HTAC, and boric acid was discussed by FTIR and element analysis. The thermal stability and surface morphology of the finished cotton fabrics were investigated by thermogravimetric analysis (TGA) and scanning electron microscope (SEM), respectively. The finishing system of the mixture containing boron and nitrogen showed excellent synergistic flame retardancy for cotton fabric. The cotton fabric finished with mixture system had excellent flame retardancy. The LOI value of the treated cotton fabric increased over 27.5. Tri-HTAC could form covalent bonds with cellulose fiber and boric acid. The flame retardant cotton fabric showed a slight decrease in tensile strength and whiteness. The surface morphology of flame retardant cotton fiber was smooth.     

Low-fouling, biofunctionalized, and biodegradable click capsules

We report the synthesis of covalently stabilized hollow capsules from biodegradable materials using a combination of click chemistry and layer-by-layer (LbL) assembly. The biodegradable polymers poly(L-lysine) (PLL) and poly(L-glutamic acid) (PGA) were modified with alkyne and azide moieties. Linear film buildup was observed for both materials on planar surfaces and colloidal silica templates. A variation of the assembly conditions, such as an increase in the salt concentration and variations in pH, was shown to increase the individual layer thickness by almost 200%. The biodegradable click capsules were analyzed with optical microscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM). Capsules were uniform in size and had a regular, spherical shape. They were found to be stable between pH 2 and 11 and showed reversible, pH-responsive shrinking/swelling behavior. We also show that covalently stabilized PLL films can be postfunctionalized by depositing a monolayer of heterobifunctional poly(ethylene glycol) (PEG), which provides low-fouling properties and simultaneously enhances specific protein binding. The responsive, biodegradable click films reported herein are promising for a range of applications in the biomedical field.     

Method for the preparation of stabile microencapsulated lactic acid bacteria

Summary A method to produce viable and stabile dry microorganisms for food and agricultural purposes was developed. Spray-dried, freeze-dried or liquid culture concentrates of lactic acid-producing bacteria were mixed with various bulking agents to form a homogeneous wet granulation having a water content of 35–60% (w/w). The wet granulation was extruded through a dye onto a spinning plate (350–500 rpm) of a spheronizing device which resulted in the formation of discrete spherical particles. After forming spheres, the aggregate cell particles, both coated and uncoated, were dried to a moisture level of 5–10% using a temperature below the microorganism's optimum growth temperature. The coated and uncoated products were stored at different temperatures and periodically sampled to determine stability. Uncoated cell particles were more stabile at 4°C than at 22°C for 76 days. While both coated (with sodium alginate or carboxymethyl-cellulose) and uncoated particles showed similar stability at 4°C, at higher storage temperatures the applied coating improved the storage stability of the culture particles.     

In Vivo Corrosion Resistance of Ca-P Coating on AZ60 Magnesium Alloy

Magnesium-based alloys are frequently reported as potential biodegradable orthopedic implant materials. Controlling the degradation rate and mechanical integrity of magnesium alloys in the physiological environment is the key to their applications. In this study, calcium phosphate (Ca-P) coating was prepared on AZ60 magnesium alloy using phosphating technology. AZ60 samples were immersed in a phosphating solution at 37 ± 2 °C for 30 min, and the solution pH was adjusted to 2.6 to 2.8 by adding NaOH solution. Then, the samples were dried in an attemperator at 60 °C. The degradation behavior was studied in vivo using Ca-P coated and uncoated magnesium alloys. Samples of these two different materials were implanted into rabbit femora, and the corrosion resistances were evaluated after 1, 2, and 3 months. The Ca-P coated samples corroded slower than the uncoated samples with prolonged time. Significant differences (p < 0.05) in mass losses and corrosion rates between uncoated samples and Ca-P coated samples were observed by micro-computed tomography. The results indicate that the Ca-P coating could slow down the degradation of magnesium alloy in vivo.     

Biomedical applications of electrostatic layer-by-layer nano-assembly of polymers,enzymes, and nanoparticles

The introduction of electrostatic layer-by-layer (LbL) self-assembly has shown broad biomedical applications in thin film coating, micropatterning, nanobioreactors, artificial cells, and drug delivery systems. Multiple assembly polyelectrolytes and proteins are based on electrostatic interaction between oppositely charged layers. The film architecture is precisely designed and can be controlled to 1-nm precision with a range from 5 to 1000 nm. Thin films can be deposited on any surface including many widely used biomaterials. Microencapsulation of micro/nanotemplates with multilayers enabled cell surface modification, controlled drug release, hollow shell formation, and nanobioreactors. Both in vitro and in vivo studies indicate potential applications in biology, pharmaceutics, medicine, and other biomedical areas.     

Graphene Multilayer Supported Gold Nanoparticles for Efficient Electrocatalysts Toward Methanol Oxidation

This study reports a simple method of integrating electroactive gold nanoparticles (Au NPs) with graphene oxide (GO) nanosheet support by layer‐by‐layer (LbL) assembly for the creation of 3‐dimensional electrocatalytic thin films that are active toward methanol oxidation. This approach involves the alternating assembly of two oppositely charged suspensions of Au NPs with GO nanosheets based on electrostatic interactions. The GO nanosheets not only serve as structural components of the multilayer thin film, but also potentially improve the utilization and dispersion of Au NPs by taking advantages of the high catalytic surface area and the electronic conduction of graphene nanosheets. Furthermore, it is found that the electrocatalytic activity of the multilayer thin films of Au NPs with graphene nanosheet is highly tunable with respect to the number of bilayers and thermal treatment, benefiting from the advantageous features of LbL assembly. Because of the highly versatile and tunable properties of LbL assembled thin films coupled with electrocatalytic NPs, we anticipate that the general concept presented here will offer new types of electroactive catalysts for direct methanol fuel cells.     

Chitosan coated alginate beads for the survival of microencapsulated Lactobacillus plantarum in pomegranate juice

This work studied the effect of multi-layer coating of alginate beads on the survival of encapsulated Lactobacillus plantarum in simulated gastric solution and during storage in pomegranate juice at 4°C. Uncoated, single and double chitosan coated beads were examined. The survival of the cells in simulated gastric solution (pH 1.5) was improved in the case of the chitosan coated beads by 0.5-2 logs compared to the uncoated beads. The cell concentration in pomegranate juice after six weeks of storage was higher than 5.5logCFU/mL for single and double coated beads, whereas for free cells and uncoated beads the cells died after 4 weeks of storage. In simulated gastric solution, the size of the beads decreased and their hardness increased with time; however, the opposite trend was observed for pomegranate juice, indicating that there is no correlation between cell survival and the hardness of the beads.     

Nano photo scouring and nano photo bleaching of raw cellulosic fabric using nano TiO2

Photo catalytic action of nano TiO(2) for decomposing of some organic compounds is a well known phenomenon. This can be extended to the application on nano TiO(2) on the desized cotton fabric to decompose the hydrophobic impurities and coloring matters of the fabric. This can be nominating as a replacement for the conventional scouring and bleaching processes on cotton fabric producing the hydrophilic white cotton fabric. The photo activities of the nano TiO(2) on the desized cotton through decomposition of the cotton impurities compared for two different light exposures: UV rays and daylight. The desized cotton fabrics treated in the ultrasonic bath containing a colloidal aqueous solution of nano TiO(2)/citric acid (CA)/sodium hypophosphite (SHP). Incorporating CA in the treatment bath enhanced the treatment durability against washing, created a durable hydrophilic white cotton fabric even after several successive washings. Increasing the nano TiO(2) content enhanced the fabric hydrophilicity and whiteness features. Overall, the nano photo scouring and nano photo bleaching on the cotton fabric introduced and thoroughly discussed. This gains the application of nano TiO(2) on textile materials besides the other well known characteristics obtained on the textiles including self-cleaning, antibacterial and UV protection.     

Hydrocolloid coating of Xenopus laevis embryos

A novel technology for coating single cells and embryos with thin hydrocolloid (water-soluble polymer) films has been invented and patented. Coating is different from entrapment and immobilization in that the coating around the cell is thinner, comprising only a small fraction of the cell or embryo's diameter. Xenopus laevis embryos were coated with thin films of low-methoxy pectin (LMP), alginate, and iota- and kappa-carrageenans. These gums have different compositions and structures and as such created different coatings around the fertilized cells. All coated embryos appeared to develop normally, similar to noncoated embryos. Elemental detection by ICP-AES spectroscopy revealed that the embryo can control the diffusion of excess ions to which it is exposed during the coating process. The coatings delayed hatching by 18-24 h. Consequently, at hatch the embryos were at a more developed stage than their noncoated counterparts. The hydrocolloid coating reduced the thickness of the natural jelly coating (JC). With the iota-carrageenan coating, percent hatch was maximal, while with LMP it was minimal, as a result of the films' mechanical properties and thicknesses. LMP and alginate created smoother coatings than the carrageenans. Potential interactions between the coating and the natural JC are hypothesized. Overall, coatings appear to be a suitable tool for laboratories interested in performing longer-term experiments with embryos.     

Layer-by-Layer coated tyrosinase: An efficient and selective synthesis of catechols

Agaricus bisporous tyrosinase was immobilized on commercial available epoxy-resin Eupergit®C250L and then coated by the Layer-by-Layer method (LbL). The two novel heterogeneous biocatalysts were characterized for their morphology, pH and storage stability, kinetic properties (K_m, V_max, V_max/K_m) and reusability. These biocatalysts were used for the efficient and selective synthesis of bioactive catechols under mild and environmental friendly experimental conditions. Ascorbic acid was added in the reaction medium to inhibit the formation of ortho-quinones, thus avoiding the known enzyme suicide inactivation process. Catechols were obtained mostly in quantitative yields and conversion of substrate. Tyrosinase immobilized on Eupergit®C250L and coated by the LbL method showed better catalytic activities, higher pH and storage stability, and reusability with respect to immobilized uncoated tyrosinase. Since chemical procedures to synthesize catechols are often expensive and with high environmental impact, the use of immobilized tyrosinase represents an efficient alternative for the preparation of this family of bioactive compounds.     

Wearable All‐Fabric‐Based Triboelectric Generator for Water Energy Harvesting

Realizing energy harvesting from water flow using triboelectric generators (TEGs) based on our daily wearable fabric or textile has practical significance. Challenges remain on methods to fabricate conformable TEGs that can be easily incorporated into waterproof textile, or directly harvest energy from water using hydrophobic textile. Herein, a wearable all‐fabric‐based TEG for water energy harvesting, with additional self‐cleaning and antifouling properties is reported for the first time. Hydrophobic cellulose oleoyl ester nanoparticles (HCOENPs) are prepared from microcrystalline cellulose, as a low‐cost and nontoxic coating material to achieve superhydrophobic coating on fabrics, including cotton, silk, flax, polyethylene terephthalate (PET), polyamide (nylon), and polyurethane. The resultant PET fabric‐based water‐TEG can generate an instantaneous output power density of 0.14 W m^?2 at a load resistance of 100 MΩ. An all‐fabric‐based dual‐mode TEG is further realized to harvest both the electrostatic energy and mechanical energy of water, achieving the maximum instantaneous output power density of 0.30 W m^?2. The HCOENPs‐coated fabric provides excellent breathability, washability, and environmentally friendly fabric‐based TEGs, making it a promising wearable self‐powered system.     

Encapsulation performance of layer-by-layer microcapsules for proteins

This study reports on the encapsulation efficiency of proteins in dextran sulfate/poly-L-arginine-based microcapsules, fabricated via layer-by-layer assembly (LbL). For this purpose, radiolabeled proteins are entrapped in CaCO(3) microparticles, followed by LbL coating of the CaCO(3) cores and subsequent dissolving of the CaCO(3) using EDTA. To allow to improve protein encapsulation in LbL microcapsules, we studied all steps in the preparation of the microcapsules where loss of protein load might occur. The encapsulation efficiency of proteins in LbL microcapsules turns out to be strongly dependent on both the charge and molecular weight of the protein as well as on the number of polyelectrolyte bilayers the microcapsules consist of.     

Antimicrobial activity of AgCl embedded in a silica matrix on cotton fabric

An antimicrobial finishing for cotton fabric was prepared from commercial (iSys AG, Germany) silver chloride (Ag) dispersed at different concentrations in a reactive organic–inorganic binder (RB) (iSys MTX (CHT, Germany). Pad-dry-cure and exhaustion methods were used for the sols application, giving Ag-RB coating with Ag concentration from ca. 48 to ca. 290 ppm on the cotton fabric. The presence of silver on the cotton finishes was confirmed by measuring its concentration in the fabrics with the help of inductively coupled plasma mass spectroscopy (ICP-MS). The morphology of the finished fabrics was investigated by SEM, while their composition was established from EDXS measurements combined with the results of FT-IR spectral analysis. The antimicrobial activity of variously treated cotton fabrics was assessed before and after repetitive (up to 10×) washing by the application of standard tests: for the fungi Aspergillus niger (ATCC 6275) and Chaetomium globosum (ATCC 6205) by the modified DIN 53931 standard method, while the presence of Gram-negative bacterium Escherichia coli (ATCC 25922) was followed by using ISO 20645:2004 (E) and AATCC 100-1999 standard methods. Results revealed that the antimicrobial activity of the coatings strongly depended on the concentration of Ag in the corresponding Ag-RB dispersions, indirectly depending on the preparation method (pad-dry-cure vs. exhaustion) and that the Ag-RB coatings were more effective for bacteria than for fungi. The Ag concentrations on the cotton fabrics achieved by the pad-dry-cure method (48 and 52 ppm) were not sufficient to impart satisfactory antifungal activity to the cotton fabrics, though they assured excellent reduction of the bacterium E. coli (98–100%). A minimal inhibitory concentration of Ag in the coating providing a sufficient bacterial reduction of 60% was ca. 24 ppm. Effective antifungal activity was achieved only by applying the exhaustion method, enabling high initial Ag concentration in the Ag-RB coating (>100 ppm). The antibacterial activity depended on the washing treatment. No antifungal activity was noted for washed cotton fabric, even those with highly concentrated Ag (290 ppm) in the Ag-RB coating, but a 94% bacterial reduction was obtained for the corresponding cotton fabric, after 10 repetitive washings, corroborated by the Ag concentration on washed fabric of about 65 ppm.     

慢性缺氧对大鼠肺动胍内皮依赖性舒张反应及CGMP含量的影响

This experiment was designed to investigate whether chronic hypoxia affect rat pulmonary artery (PA) endothelium-dependent relaxation and the content of cGMP in PA. Both ACh and ATP could induce endothelium-dependent relaxation of PA, not prevented by indomethacin, but completely abolished by methylene blue. These results indicated that vasodilatation of PA induced by both ACh and ATP is mediated by EDRF (endothelium-derived relaxing factor). Chronic hypoxia significantly depressed PA endothelium-dependent relaxation. The percent relaxation of IPPA and EPPA by 10(-6) mol/L ACh was 61.3% and 59.2% of those in control, and the percent relaxation of IPPA and EPPA by 1.8 x 10(-5) mol/L ATP was 64.9% and 55.3% respectively of the control. Chronic hypoxia also depressed SNP-induced endothelium-independent relaxation. Chronic hypoxia significantly decreased the content of cGMP in PA. The basic level of cGMP was 51.9 +/- 5.7 (n = 14) in hypoxia group and 84.9 +/- 9.7 (n = 14) pmol/g wet wt. in control group (P less than 0.01). After treatment of PA with ACh (10(-7) mol/L), the content of cGMP was 91.4 +/- 7.3 (n = 5) pmol/g wet wt. in hypoxic group and 240.8 +/- 30.6 (n = 5) pmol/g wet wt. in control group (P less than 0.01). Our data suggest that chronic hypoxia might depress rat pulmonary artery endothelium-dependent relaxation through the inhibition of soluble guanylate cyclase in vascular smooth muscle cells.     

Does waterproofing Thermochron iButton dataloggers influence temperature readings?

Miniature Thermochron iButton dataloggers have transformed the ways in which researchers collect thermal data. However, one important limitation is that these dataloggers are not waterproof, which can lead to device failure and loss of data under field conditions. Several methods have been used to increase their water resistance, but no study to date has investigated whether any of these techniques affects the accuracy of temperature readings. Waterproofing potentially could affect the accuracy of iButtons by biasing temperatures or altering rates of warming and cooling. We compared temperature profiles of unmodified Thermochron iButtons (model DS1921G) to iButtons that we coated with a clear plastic dip (designed to coat tool handles) to determine whether this waterproof coating affects the accuracy of temperatures they record. We also compared temperatures recorded by uncoated and coated iButtons that were embedded within physical models that mimic frog body temperatures. Finally, we used our field data to test whether coating iButtons with plastic prevents failure of dataloggers during fieldwork. Although we found statistically significant differences between the temperatures recorded by uncoated and coated iButtons, and also between uncoated and coated iButtons embedded in frog models, these effects were relatively small (0–1.3 °C). We also found that coating iButtons with plastic reduced the likelihood of device failure under field conditions (from 8.3% to 0%). We conclude that coating Thermochron iButtons with plastic is an affordable and reliable method of waterproofing dataloggers that prevents device failure and data loss with minimal influence on temperature readings.