Ionic polysaccharides. II. Comparison of polyelectrolyte behavior of hyaluronate with that of carboxymethyl cellulose

Sodium hyaluronate (NaHy) and sodium carboxymethyl cellulose (NaCMC) behave similarly with respect to concentration.N ₃ of an added 1 : 1 electrolyte. The second virial coefficient A₂ (light scattering) is identical within experimental error at a given.N ₃. The limiting viscosity number [η] also varies with N₃^?1/2in similar fashion for samples of similar [η] of the two polymers. Differences in Na⁺ activity in salt-free solutions are interpreted on the basis of weaker Na⁺ binding in NaHy, presumably due to the greater charge separation along its chain backbone. Added electrolyte is excluded in dialysis more strongly by NaHy (or its acid form) than by NaCMC. The Flory parameter Φ is smaller in good solvents for NaHy, as for many other polyelectrolytes, than for nonionic polymers.     

Biodegradable cellulose diacetate-graft-poly(L-lactide)s: enzymatic hydrolysis behavior and surface morphological characterization

Enzymatic hydrolysis of selected copolymers of cellulose diacetate-graft-poly(L-lactide)s (CDA-g-PLLAs) were conducted with proteinase K for film specimens, which were solely quenched from the molten state or, further, annealed at temperatures below or above their glass transition temperatures. The hydrolysis rates depended seriously on the thermal history, as well as on the graft modification. Especially, the heat treatment, followed by physical aging or crystallization of the originally amorphous materials, was a key factor to control subtly their enzymatic degradation behavior. Atomic force microscopy revealed that the enzymatic hydrolysis transformed the surface of the respective films into a more undulated one with a number of fine protuberances, for example, of several hundred nanometers in height and a few micrometers in width. Attenuated total reflection FTIR spectroscopy ensured selective release of lactyl units from the surface region. In visual appearance, some degraded films exhibited even an iridescent color due to an effect of interference of visible light reflected on the surface. These observations suggest a conception of "spatiotemporally controlled degradation", leading to a new method not only for regulation of the overall rate of degradation but also for fine surface abrasion of polymer materials.     

Phosphate removal by refined aspen wood fiber treated with carboxymethyl cellulose and ferrous chloride

Biomass-based filtration media are of interest as an economical means to remove pollutants and nutrients found in stormwater runoff. Refined aspen wood fiber samples treated with iron salt solutions demonstrated limited capacities to remove (ortho)phosphate from test solutions. To provide additional sites for iron complex formation, and thereby impart a greater capacity for phosphate removal, a fiber pretreatment with an aqueous solution of a non-toxic anionic polymer, carboxymethyl cellulose (CMC), was evaluated. Problems with excessive viscosities during the screening of commercially available CMC products led to the selection of an ultra low viscosity CMC product that was still usable at a 4% concentration in water. Soxhlet extractions of chipped aspen wood and refined aspen wood fiber samples showed a higher extractives content for the refined material. Analysis of these extracts by FTIR spectroscopy suggested that the higher extractives content for the refined material resulted from the fragmentation of cell wall polymers (e.g., lignin, hemicelluloses) normally insoluble in their native states. Spectroscopic analysis of CMC and ferrous chloride treated fibers showed that the complex formed was sufficiently stable to resist removal during subsequent water washes. Equilibrium sorption data, which fit better with a Freundlich isotherm model than a Langmuir isotherm model, showed that phosphate removal could be enhanced by the CMC pretreatment. Results suggest that the process outlined may provide a facile means to improve the phosphate removal capacity of biomass-based stormwater filtration media.     

Structural characterization of self-assembled polypeptide films on titanium and glass surfaces by atomic force microscopy

Chemically modified biomaterial surfaces (titanium and glass) covered with polyelectrolyte self-assembled films formed by the alternating adsorption of cationic poly-L-lysine (PLL) and anionic poly-L-glutamic acid (PGA) were structurally characterized by atomic force microscopy. Complementary information concerning the thickness and layer-by-layer growth of the films was provided by optical waveguide light-mode spectroscopy. The frequently used ex situ and the rarely used in situ build-up methods were compared. Important aspects of the industrial applicability of these films, their stability in time, and possible differences in their morphology were investigated. The films revealed a granular pattern, with grain diameters of 270 +/- 87 nm for glass (up to 8 bilayers) and 303 +/- 89 nm for titanium (up to 10 bilayers), independently of the build-up procedure. Both surfaces displayed a rehydration capability, the titanium surface exhibiting a better stability in time. The high roughness values observed at acidic or basic pH are related to the degree of ionization of PGA and PLL.     

Preparation and characterization of persimmon leaves/cellulose blend fiber and comparison with cellulose fiber

With respect to the fact that persimmon leaves having better effects on medical area applications, a persimmon leaves/cellulose blend fiber was prepared by wet spinning from a DMSO/polyoxymethylene solvent under different spinning conditions, e.g. the temperature of coagulation bath, amount of persimmon leaves added and concentration of spinning solution. Based on mechanical measurement, X-ray diffraction and DSC characterization, it was found that this blend fiber had similar mechanical and thermal properties as referenced cellulose fiber obtained using the same method.     

Amino-functionalized cellulose nanoparticles: preparation, characterization, and interactions with living cells

Spherical nanoparticles with sizes from 80 to 200 nm are obtained by self-assembly of highly functionalized 6-deoxy-6-(ω-aminoalkyl)aminocellulosecarbamates. The particles are very stable, nontoxic, and possess primary amino groups that are accessible to further modifications in aqueous suspension. The particles can be labeled with rhodamine B isothiocyanate without changing their size, stability, and shape. The nanoparticles obtained are investigated by means of photo correlation spectroscopy, zeta potential measurements, SEM and fluorescence spectroscopy. Incorporation of the nanoparticles in human foreskin fibroblasts BJ-1-htert and breast carcinoma MCF-7 cells without any transfection reagent is proved by means of confocal laser scanning microscopy.     

Alpha-chymotrypsin immobilized on ferromagnetic particles coated with titanium oxide: production and catalytic properties

Immobilization of alpha-chymotrypsin on magnetic particles with stable coat with titanium oxides as a main constituent allowed the biocatalytic system to be quickly and qualitatively separated into the components after completion of the enzymatic reaction. X-ray phase analysis demonstrated that the coat of magnetic particles is composed mainly of titanium dioxide in brookite modification. The maximal capacity of the particles amounted to 0.3 mg protein/mg particles. It was demonstrated that the reaction catalyzed by immobilized alpha-chymotrypsin proceeds in a kinetic mechanism due to a high dispersion of the ferromagnetic particles. The catalytic constant (25 s-1) and KM (0.17 mM) for the immobilized enzyme for the hydrolysis of N-acetyl-L-tyrosine ethyl ester are comparable to the corresponding characteristics for the free enzyme.     

Ionic conjugates of sulfate carboxymethyl cellulose with dialkylaminomethyl derivatives of 2-isobornyl-4-methylphenol: Synthesis and study of anti-inflammatory and analgesic activity

Water-soluble sulfate polysalts of carboxymethyl cellulose and tertiary aminomethyl derivatives of 2-isobornyl-4-methylphenol were obtained. Investigations were carried out for the synthesized conjugates in vivo of anti-inflammatory activity in the test for acute formalin inflammation and analgesic activity in the ??hot plate?? and ??acetic acid writhings?? tests.     

Dendronized hydroxypropyl cellulose: synthesis and characterization of biobased nanoobjects

Dendronized polymers containing a cellulose backbone have been synthesized with the aim of producing complex molecules with versatile functionalization possibilites and high molecular weight from biobased starting materials. The dendronized polymers were built by attaching premade acetonide-protected 2,2-bis(methylol)propionic acid functional dendrons of generation one to three to a hydroxypropyl cellulose backbone. Deprotection or functionalization of the end groups of the first generation dendronized polymer to hydroxyl groups and long alkyl chains was performed, respectively. The chemical structures of the dendronized polymers were confirmed through analysis using (1)H NMR and FT-IR spectroscopies. From SEC analysis, the dendronized polymers were found to have an increasing polystyrene-equivalent molecular weight up to the second generation ( M n = 50 kg mol (-1)), whereas the polystyrene-equivalent molecular weight for the third generation was lower than for the second, although the same grafting density was obtained from (1)H NMR spectroscopy for the second and third generations. Tapping-mode atomic force microscopy was used to characterize the properties of the dendronized polymers in the dry state, exploring both the effect of the polar substrate mica and the less polar substrate highly oriented pyrolytic graphite (HOPG). It was found that the molecules were in the size range of tens of nanometers and that they were apt to undertake a more elongated conformation on the HOPG surfaces when long alkyl chains were attached as the dendron end-groups.     

Radical graft functional modification of cellulose with allyl monomers: Chemistry and structure characterization

Cotton cellulose was successfully functionalized via a free radical graft polymerization process. Potassium persulfate served as an effective water soluble radical initiator to generate cellulosic radicals. The polymeric radicals could react with allyl monomers such as allyl-dimethylhydantion (ADMH) to form surface grafted cellulose. The reaction sites generated by potassium persulfate were probably at carbon 3 and 4 in glucose ring via oxidative hydrogen abstraction. The cellulosic radicals can initiate grafting polymerization of ADMH with a maximum polymerization degree of about 12 based on LC–MS results. The radical graft polymerization mechanisms were proposed based on LC–ESI/MS analysis. The ideal covalent bonding between cellulose and poly (allyl-dimethylhydantion) (PADMH) ensured permanent graft of the monomers on cotton and durability of the expected functions on the treated cotton.     

Gas holdup and mass transfer characteristics of carboxymethyl cellulose solutions in a bubble column with a radial gas sparger

The gas phase holdup and mass transfer characteristics of carboxymethyl cellulose (CMC) solutions in a bubble column having a radial gas sparger have been determined and a new flow regime map has been proposed. The gas holdup increases with gas velocity in the bubbly flow regime, decreases in the churn-turbulent flow regime, and increases again in the slug flow regime. The volumetric mass transfer coefficient (k _La) significantly decreases with increasing liquid viscosity. The gas holdup and k _La values in the present bubble column of CMC solutions are found to be much higher than those in bubble columns or external-loop airlift columns with a plate-type sparger. The obtained gas phase holdup ( _g) and k _La data have been correlated with pertinent dimensionless groups in both the bubbly and the churn-turbulent flow regimes.List of Symbols a m^–1 specific gas-liquid interfacial area per total volume - A _d m² cross-sectional area of downcomer - A _r m² cross-sectional area of riser - d _b m individual bubble diameter - d _vs m Sauter mean bubble diameter - D _c m column diameter - D _L m²/s oxygen diffusivity in the liquid - Fr Froude number, U _g/(g D_c)^1/2 - g m/s² gravitational acceleration - G _a Galileo number, gD _c ^{3 2}/² _app - H _a m aerated liquid height - H _c m unaerated liquid height - K Pa · sⁿ fluid consistency index - k _L a s^–1 volumetric mass transfer coefficient - n flow behavior index - N _i number of bubbles having diameter d _bi - Sc Schmidt number, _app/( D _L) - Sh Sherwood number, k _L a D _c ² /D_L - U _sg m/s superficial gas velocity - U _gr m/s superficial riser gas velocity - V _a m³ aerated liquid volume - V _c m³ unaerated liquid volume - N/m surface tension of the liquid phase - _g gas holdup - _app Pa · s effective viscosity of non-Newtonian liquid - kg/m³ liquid density - ý s^–1 shear rate - Pa shear stress     

Nonfouling behavior of polycarboxybetaine-grafted surfaces: structural and environmental effects

Zwitterionic carboxybetaine (CB) has unique dual functionality for ligand immobilization on a nonfouling background. The properties of CB groups depend on their spacer groups between the positive quaternary amine groups and the negative carboxyl groups and environmental factors (e.g., ionic strengths and pH values). In this work, five polycarboxybetaines were prepared, including one polycarboxybetaine methacrylate (polyCBMA) and four polycarboxybetaine acrylamides (polyCBAAs) with different spacer groups. The polymers were grafted from a gold surface covered with initiators using surface-initiated atom transfer radical polymerization. Fibrinogen adsorption was measured as a function of ionic strengths and pH values using surface plasmon resonance sensors. The responsive protein adsorption on four polyCBAAs was mapped out. Results show that most of these surfaces exhibit high protein resistance in a wide range of ionic strengths and are more effective than zwitterionic self-assembled monolayers. Although protein adsorption tends to increase at low ionic strength and low pH value, it is still very low for polycarboxybetaines with a methylene, an ethylene, or a propylene spacer group but is more evident for polyCBAA with a longer spacer group (i.e., a pentene group). The response to ionic strengths and pH values can be attributed to the antipolyelectrolyte and protonation/deprotonation properties of polycarboxybetaines, respectively. Both of these properties are related to the spacer groups of CBs.     

Functionalization of cotton fabrics with titanium oxide doped silver nanoparticles: Antimicrobial and UV protection activities

The target of our current work was designed to prepare titanium oxide doped silver nanoparticles (Ag/TiO₂NPs) and their impact on the functionalization of cotton fabrics. Additionally, the effect of Ag/TiO₂NPs was compared with the individually prepared silver nanoparticles (AgNPs) and titanium oxide nanoparticles (TiO₂NPs). In this work, AgNPs were prepared in the solid state using arabic gum as efficient stabilizing and reducing agent. Then, two concentrations of the as-synthesized nanoparticles were used to functionalize the cotton fabrics by pad-dry-cure treatment in the presence of fixing agent to increase the durability of treated cotton fabrics against vigorous washing cycles. The findings implied that the as-prepared nanoparticles were successfully synthesized in nano-size with spherical shape and homogeneity. The efficacy of the functionalized cotton fabrics with those nanoparticles were evaluated in terms of multifunctional properties including antimicrobial and ultraviolet protection factor (UPF) and the mechanical features before and after many washing cycles; 10, 15 and 20 times. The resultant also proved that Ag/TiO₂NPs-treated cotton fabrics exhibited the greater values of both antimicrobial and UPF properties with enhancement in the tensile strength and elongation features. Thus, the combination between these two nanoparticles through doping reaction is suitable for imparting superior antimicrobial properties against the four tested microbial species (Staphylococcus aureus, Escherichia coli, Candida albicans, and Aspergillus niger) and good UPF properties. Depending on the promising obtained results of the multi-finishing fabrics, these nanoparticles of Ag/TiO₂NPs can be applied for the production of an efficient medical clothes for doctors, nurses and bed sheets for patients in order to kill and prevent the spread of bacteria and then, reduce the transmission of infection to others.     

Synthesis and characterization of cellulose/silica hybrid materials with chemical crosslinking

The cellulose/silica hybrid biomaterials are prepared by sol–gel covalent crosslinking process. The tetraethoxysilane (TEOS) as precursor, γ-aminopropyltriethoxylsilane (APTES) as couple agent, and 2,4,6-tri[(2-epihydrin-3-bimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-EBAC) as crosslinking agent, are used in the sol–gel crosslinking process. The chemical and morphological structures of cellulose/silica covalent crosslinking hybrids are investigated with micro-FT-IR spectra, nitrogen element analysis, X-ray diffraction, SEM, AFM, and DSC. The results show that the cellulose/silica hybrids form new macromolecular structures. In sol–gel process, inorganic particles are dispersed at the nanometer scale in the cellulose host matrix, bounding to the cellulose through covalent bonds. The cellulose/silica covalent crosslinking hybrid can form good and smooth film on the cellulose. The thermal properties of organic/inorganic hybrids are improved.     

Preparation and characterization of durable antibacterial cellulose biomaterials modified with triazine derivatives

Cellulose fabric was chemically modified with the triazine derivatives containing the multi-cationic benzyl groups. The novel durable antibacterial cellulose biomaterial containing the multi-cationic benzyl groups was prepared. The chemical structure and thermal property of the antibacterial cellulose biomaterial were investigated with FT-IR spectra, nitrogen content analysis, and differential scanning calorimetry (DSC). The results show that the thermal stability of the novel antibacterial cellulose was slightly decreased. Physical properties of the novel antibacterial cellulose had not significant change. The novel antibacterial cellulose imparted excellent durable antibacterial properties.     

Alterations in the adhesion behavior of osteoblasts by titanium particle loading: inhibition of cell function and gene expression

Total joint replacement prostheses are required to withstand corrosive environments and sustain millions of loading and articulation cycles during their term of implantation. Wear debris generation has been implicated as one of the primary causes of periprosthetic osteolysis and subsequent implant loosening in total joint replacements. Particulate debris consisting of metals, polyethylene, ceramics, and bone cement have each been shown to provoke a biological response in joint tissues. The major cell types within the interfacial granulomatous fibrous tissues consist of fibroblasts, macrophages, lymphocytes, and foreign-body giant cells. Osteoblasts are one of the principal cell types in the bone tissue adjacent to prostheses, maintaining physiologic bone remodeling through the balanced coordination of bone formation and resorption in concert with osteoclasts. To date the phenomenon of osteoblast phagocytosis of titanium particles has been suggested, but has not been sufficiently studied or confirmed. This study seeks to clarify the influence of titanium particles on osteoblast adhesion, deformability, proliferation, and gene expression profile. These studies were accomplished by performing biorheological testing, Northern blot analysis and RNase protection assay. The uptake of metallic particles by the osteoblast resulted in a particle-filament complex formation, which induced a series of variations in cell function. Understanding these variations is critical to expanding our knowledge of implant loosening and elucidating the nature of prosthetic joint failure. This study suggests that the impact of titanium particles on osteoblast function and subsequent implant loosening may have been previously underestimated.     

Functionalized nanocrystal-tagged fluorescent polymer beads: synthesis, physicochemical characterization, and immunolabeling application

A methodology for incorporating solubilized CdSe/ZnS core/shell nanocrystals (NCs) into functionalized carboxylated polystyrene latexes 0.3-1 microm in diameter via a swelling procedure was developed and used for the production of homogeneous, highly fluorescent polymeric beads (HFPBs), which were found to be comparable in brightness to standard polymeric microspheres doped with organic fluorophores and more photostable than the latter by more than 50 times (Fluoresbrite yellow-orange microspheres were used as an example). The three-dimensional (3D) confocal analysis of individual 1-microm HFPB demonstrated that the beads were doped with the NCs almost homogeneously. HFPBs 0.3 microm in diameter were conjugated with anti-mouse polyvalent immunoglobulins and used for immunofluorescent detection of p-glycoprotein, a mediator of the multidrug resistance phenotype, overexpressed in the membrane of MCF7r breast adenocarcinoma cells. The photostability of NCs-tagged HFPBs offers obvious advantages for the reconstruction of 3D confocal fluorescence images of antigen distribution, and their exceptionally high brightness combined with photostability permits the detection of a single antigen molecule using a standard epifluorescence microscope.     

Effect of biofouling on anodized and sol-gel treated titanium surfaces: a comparative study

Anodization and sol-gel treatments of titanium (Ti) were evaluated as biofilm control measures on surfaces exposed to seawater exposed to ultraviolet light. Anodized and sol-gel treated specimens were characterized using Raman spectroscopy to confirm the presence of TiO(2). The single anatase phase was observed at the anodized surfaces whereas the anatase/rutile mixed phase was detected on the sol-gel coated surfaces. After exposure of the specimens to seawater, biofilms were characterized by total viable counts, and epifluorescence and Raman microscopy. These techniques confirmed the reduction in biofilm formation on both the anodized and sol-gel coated Ti specimens compared to the untreated specimens. Biofilm control by anodization was found to be more effective than by sol-gel treatment of the specimens. The higher particle size and the inhomogeneity at the sol-gel coated surfaces produced less effective biofilm control.     

Effect of biofouling on anodized and sol-gel treated titanium surfaces: a comparative study

Anodization and sol-gel treatments of titanium (Ti) were evaluated as biofilm control measures on surfaces exposed to seawater exposed to ultraviolet light. Anodized and sol-gel treated specimens were characterized using Raman spectroscopy to confirm the presence of TiO₂. The single anatase phase was observed at the anodized surfaces whereas the anatase/rutile mixed phase was detected on the sol-gel coated surfaces. After exposure of the specimens to seawater, biofilms were characterized by total viable counts, and epifluorescence and Raman microscopy. These techniques confirmed the reduction in biofilm formation on both the anodized and sol-gel coated Ti specimens compared to the untreated specimens. Biofilm control by anodization was found to be more effective than by sol-gel treatment of the specimens. The higher particle size and the inhomogeneity at the sol-gel coated surfaces produced less effective biofilm control.