Chemical functionalization of chitosan biopolymer and chitosan-magnetite nanocomposite with sulfonic acid for acid-catalyzed reactions

Chemical functionalization of chitosan biopolymer and chitosan-magnetite nanocomposite was performed with sulfonic acid functional groups to achieve new solid acid materials. The sulfonic acid functional groups were created through the ring opening nucleophilic reaction of amine groups of chitosan with 1,4-butane sultone. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopies (XPS) verified the successful sulfonic acid functionalization of chitosan. The obtained sulfonic acid functionalized chitosan-magnetite nanocomposite showed superparamagnetic properties according to the vibrating sample magnetometry analysis and exhibited magnetic separation feature from dispersed mixtures. Nitrogen adsorption-desorption analysis indicated the increase in surface area after formation of chitosan-magnetite nanocomposite and functionalization with sulfonic acid. Both of the prepared solid acids exhibited high catalytic activities in the acid-catalyzed acetic acid esterification with n-butanol and benzaldehyde acetalization with ethylene glycol as model reactions. Furthermore, they can be reused several times without considerable loss of their activities.     

Functionalization of nanodiamond particles with N,O-carboxymethyl chitosan

Nanodiamond (ND) particles are biocompatible with no cytotoxicity to cells and have large surface area to provide high affinity to biomolecules. These properties make nanodiamond an ideal candidate for drug delivery. Protein pharmaceuticals have been becoming powerful and indispensable in combating human diseases due to the fact that they have high specificity and activity even at relatively low concentration. The present work deals with functionalization of nanodiamond particles for protein drug delivery applications. N,O-carboxymethyl chitosan (CMCS) is employed to modify the surface properties of pristine ND particles which has been proved to be successful by a series of characterizations: Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, zeta-potential measurement, and X-ray diffraction (XRD). The interaction of CMCS modified nanodiamond particles (NDCMCS) with protein drug as well as its protein drug release properties will be studied in the next step.     

Surface and mechanical properties of an organic-inorganic super- hydrophobic coating using modified nano-SiO2 and mixing polyurethane emulsion as raw materials

A series of organic-inorganic super-hydrophobic coatings were prepared using nano-SiO₂ particles modified by fluorine and silicone coupling agents, and a mixing polyurethane emulsion as main raw materials. The mixing polyurethane emulsion was consisted of the polyurethane emulsion end-terminated by double bond (WPUD) and polyurethane emulsion modified by silicone (WPUS). The influence of content of modified nano-SiO₂ particles and the weight ratio of WPUS to WPUD on microstructure and hydrophobicity of the coating surface were studied. The morphologies of coating surface were examined using SEM and AFM, hydrophobicity of the coating was researched by examining static water contact angle and so on. It was found that modified nano-SiO₂ particle was an indispensable factor during the preparation of super-hydrophobic coating. The roughness and hydrophobicity of the coating surface were enhanced obviously with an increase of the content of the modified nano-SiO₂ particles. When the content of the modified nano-SiO₂ particles increased up to 1.5%, the surface of coating possessed good super-hydrophobicity, and static water contact angle reached 169.1°. It was also noticed that the weight ratio of WPUS to WPUD in the base layer has also an important influence on the hydrophobicity and mechanical property of coating surface. With an increase of the ratio of WPUS to WPUD the hydrophobicity of the coating was enhanced, the tensile strength and peel strength reduced, but the elongation at break increased. When the weight ratio of WPUS to WPUD reaches up to 9/100, the static water contact angle reaches the maximum value of 169.1°.     

Spray-Dried Chitosan Microspheres as a pDNA Carrier

Spray-dried chitosan microparticles with controlled size were prepared and crosslinked with the biocompatible reactant d,l-glyceraldehyde. Glutaraldehyde, the conventional cross-linking agent for proteins, was used as a control. The crosslinking degree was characterized through thermal analysis, X-ray diffraction, and infrared spectroscopy. In addition, the crosslinking effects were analyzed in terms of particle size, swelling capability, and surface charge. By properly choosing d,l-glyceraldehyde concentration and crosslink time, a high degree of control was achieved over the physical properties of particles. Yields around 78% as well as images obtained through fluorescence microscopy demonstrated the capability of the crosslinked chitosan microspheres to pDNA complexation.     

Reactive acid curing waterborne microparticles

This paper describes and evaluates different techniques for introducing acetal functional groups on waterborne microparticles. Aqueous dispersions of microparticles consisting of 70 wt.% styrene and 30 wt.% ethylacrylate were prepared by emulsion polymerization. Copolymer particles and core-shell particles were produced. The particle diameters were varied in the range from about 50 to 150 nm. The particles surfaces were modified by introducing an acetal functionality. Surface functionalization was performed in two different ways. Surface reactivity was introduced by the use of an acetal functional group containing an acrylic monomer in the polymerization step. The acetal functional groups were also introduced through post-polymerization grafting techniques. The particle surfaces were modified by introducing an acetal functionality, suitable for waterborne acid curing binder systems. The functionality in question is a diacetal, which recently has proved to undergo acid catalyzed crosslinking at ambient temperatures [1]. Acetal functionalized microparticles might replace amino resins. Crosslinking between amino resins produces formaldehyde but crosslinking based on acetals does not produce formaldehyde.     

Hydrothermally treated chitosan spontaneously forms water-soluble spherical particles stable at a wide pH range

The authors report the spontaneous formation of water-soluble chitosan-tartaric acid (CS-TA) spherical particles. Particles are formed by heating chitosan in the presence of tartaric acid under hydrothermal conditions. Tartaric acid serves as an ionic cross-linker, a depolymerizing agent, and a particle stabilizer in aqueous phase. The CS-TA particles exhibit superior colloidal stability at a wide pH range due to their surface charge tunability, which is due to the colocalization of surface hydroxyl, amine, and carboxyl groups. At physiological pH condition, particles have zwitterionic structure as determined by the zeta potential measurements. Still, CS-TA maintains colloidal stability at neutral pH due to the abundance of surface hydroxyl groups. As a proof-of-concept study, the CS-TA particles were labeled with a model insoluble cargo (fluorescein isothiocyanate [FITC]) to demonstrate their capacity for solubilizing hydrophobic drugs. The CS-TA/FITC conjugates were found to remain well dispersed at neutral pH, while maintaining FITC fluorescence properties.     

Electrospinning and Photocrosslinking of Highly Modified Fungal Chitosan

The main focus of this study is to elucidate and optimize the electrospinning process for highly modified fungal chitosan. An efficient one-step process for functionalization of chitosan with arylazide and other desired functional groups via amidation is used for synthesis. Critical electrospinning process parameters, namely, molecular weight, concentration, and ratio of chitosan and additive poly(ethylene oxide) as well as degree of substitution of chitosan are identified by systematic parameter variation following design-of-experiment guidelines. Their influence on the viscoelastic properties of spinning solutions is studied and attributed to changes in chain entanglements. These changes result in drastic shifts in the electrohydrodynamic jet behavior and the resulting fiber morphologies. When the viscosity is increased above a critical limit, complete cancellation of whipping instabilities is observed, resulting in a stable linear jet and highly aligned but partly coalescing microfibers. It is shown how this process conditions can be avoided and how the production of uniform and defect-free nanofibers from highly functional chitosan can be carried out. In addition, a new photocrosslinking method for generation of water and acid stable chitosan nanofiber meshes is established.     

Covalent and Stable CuAAC Modification of Silicon Surfaces for Control of Cell Adhesion

Stable primary functionalization of metal surfaces plays a significant role in reliable secondary attachment of complex functional molecules used for the interfacing of metal objects and nanomaterials with biological systems. In principle, this can be achieved through chemical reactions either in the vapor or liquid phase. In this work, we compared these two methods for oxidized silicon surfaces and thoroughly characterized the functionalization steps by tagging and fluorescence imaging. We demonstrate that the vapor‐phase functionalization only provided transient surface modification that was lost on extensive washing. For stable surface modification, a liquid‐phase method was developed. In this method, silicon wafers were decorated with azides, either by silanization with (3‐azidopropyl)triethoxysilane or by conversion of the amine groups of an aminopropylated surface by means of the azido‐transfer reaction. Subsequently, D ‐amino acid adhesion peptides could be immobilized on the surface by use of Cu^I‐catalyzed click chemistry. This enabled the study of cell adhesion to the metal surface. In contrast to unmodified surfaces, the peptide‐modified surfaces were able to maintain cell adhesion during significant flow velocities in a microflow reactor.     

Preparation and properties of a simple super-hydrophobic carbon fiber composite surface

Super-hydrophobic surface is widely used in waterproof, antifouling, and anticorrosion fields because of its unique wetting characteristics. However, the rough structure of super-hydrophobic surface is easily damaged in service, which leads to the loss of various properties, making it difficult to apply super-hydrophobic surface on a large scale in actual production. In this paper, epoxy resin was used as adhesive, mixed with hydrophobic silica particles and sprayed on the surface of carbon fiber composites. After curing, the surface of super-hydrophobic carbon fiber composites with contact angle of 158 ± 2° and sliding angle of 1 ± 0.5° was formed. The surface had excellent dynamic water repellent performance, and the droplets could bounce more than three times on the surface. Furthermore, the super-hydrophobic surface had excellent wear resistance and mechanical stability. After the friction damage test, the surface structure of the sample was slightly damaged. The amount of wear was small, and the surface was still in super-hydrophobic state. Through soaked in solutions with different pH values, the microstructure of the surface was not obviously damaged by corrosion, the contact angle of water droplets was greater than 155°. The preparation method of super-hydrophobic surface of carbon fiber composite proposed in this study is simple and rapid, and the prepared surface has excellent performance, the practical application of super-hydrophobic surface is promoted.     

Influence of concentration of hydroxyapatite surface modifier agent on bioactive composite characteristics

The characterization of chitosan – hydroxyapatite (CH – HAp) composite sponges prepared via freeze-drying methodology is reported in this study. Stearic acid (SA), added as a surface modifier of the HAp nanoparticles, induced changes in the TG/DTG results, particle size distribution and particle morphology. Composite sponges prepared with SA coated HAp demonstrated enhanced biocompatibility and structural properties, as compared to the composites prepared with uncoated HAp. SA coating modified the morphology of the composite, promoting a better dispersion of HAp particles within the composite sponges, and better homogeneity of the polymeric cover with HAp particles. The viability of the composites for cell culture applications was analyzed, and the results suggest that the sponges are biocompatible. Therefore, SA proved to be a good candidate for surface coating of HAp nanoparticles prevent agglomerations, and could be used effectively in the preparation of biocompatible composite sponges with chitosan.     

Application of chitosan solutions gelled by melB tyrosinase to water‐resistant adhesives

An investigation was undertaken on the application of dilute chitosan solutions gelled by melB tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenethylamine (dopamine). The tyrosinase‐catalyzed reaction with dopamine conferred water‐resistant adhesive properties to the semi‐dilute chitosan solutions. The viscosity of the chitosan solutions highly increased by the tyrosinase‐catalyzed quinone conversion and the subsequent nonenzymatic reactions of o‐quinones with amino groups of the chitosan chains. The viscosity of chitosan solutions highly increased in shorter reaction times by addition of melB tyrosinase. Therefore, in this study, the gelation of a chitosan solution was carried out without poly(ethylene glycol) (PEG), which was added for the gelation of chitosan solutions using mushroom tyrosinase. The highly viscous, gel‐like modified chitosan materials were allowed to spread onto the surfaces of the glass slides, which were tightly lapped together and were held under water. Tensile shear adhesive strength of over 400 kPa was observed for the modified chitosan samples. An increase in either amino group concentration of the chitosan solutions or molecular mass of the chitosan samples used effectively led to an increase in adhesive strength of the glass slides. Adhesive strength obtained by chitosan materials gelled enzymatically was higher than that obtained by a chitosan gel prepared with glutaraldehyde as a chemical crosslinking agent. In addition, the use of melB tyrosinase led to a sharp increase in adhesive strength in shorter reaction times without other additives such as PEG. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Role of Hydrogen Peroxide in Selective OH Group Functionalization of Polypropylene Surfaces using Underwater Capillary Discharge

Plasma chemical methods are well suited for introducing functional groups to the surfaces of chemically inert polymers such as polyolefins. However, a broad variety of functional groups are often formed. Unfortunately, for further chemical processing such as grafting of molecules for advanced applications a highly dense monotype functionalized polyolefin surface is needed. Therefore, the main task was to develop a selective surface functionalization process, which formed preferably only a single type of functional groups at the surface in high concentration. Amongst the novel plasma methods, the underwater plasma process (UWP) is one of most attractive options to solve the problem of monotype functionalization. Such plasma is an efficient source of ions, electrons, UV-radiation, high-frequency shock waves, radicals such as hydroxyl radical, and reactive neutral molecules such as hydrogen peroxide. In contrast to established gas phase glow discharge processes, the water phase limits the particle and radiation energies and thus the energy input into the polymer. By virtue of the liquid water environment, which moderates highly energetic plasma species, extensive oxidation, degradation, cross-linking and radical formation on the polymer are more limited as compared to gas plasma exposure. The variety of plasma produced species in the water phase is also much smaller because of the limited reaction possibilities of the plasma with water. The possibility to admix a broad variety of chemical additives makes underwater plasma even more attractive. Hydrogen peroxide and the catalyst (Fe-ZSM5) should influence and increase the equilibrium concentration of OH radicals in the underwater plasma process. It was found that these radicals played a very important role in OH functionalization of polyolefin surfaces. Hydrogen peroxide was identified to be the most prominent precursor for OH group formation in the UWP. The catalyst would affect the steady state of OH radical formation and its reaction with the substrate surface and thus accelerates the functionalization process.     

Influence of varying surface hydrophobicity of chitosan membranes on the adsorption and activity of lipase

The hydrophobic surface modification of chitosan membranes was performed using the amidating reaction of amino groups on a membrane surface with stearic acid activated by 1‐ethyl‐3‐(3‐dimethylaminopropyl)‐carbodiimide hydrochloride (EDC) and N‐hydroxysuccinimide (NHS). The varying surface hydrophobicity of chitosan membranes was achieved by changing the degree of amidation and evaluated by the water contact angle analysis and the adsorption experiment of the hydrophobic dye, Rose Bengal. The effects of the surface hydrophobicity of chitosan membranes on the adsorption behaviors, activity and stability of Candida rugosa lipases were investigated. The experimental results suggested that the increased surface hydrophobicity of chitosan membranes improved the adsorption capacity and activity of the immobilized lipase. The modified chitosan membranes with 30.36% amidation exhibited the maximum activity retention of 83.87%. In addition, a desirable thermal stability was also achieved for the adsorbed lipase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Cisplatin-loaded carbon-encapsulated iron nanoparticles and their in vitro effects in magnetic fluid hyperthermia

Iron nanoparticles encapsulated by carbon are protected from reactions with their environment avoiding oxidation in ambient conditions and thus, preserving their magnetic properties. Such particles are good candidates for magnetic fluid hyperthermia. When graphite shells are present, acidic treatments allow the formation of carboxylic groups on the nanoparticle surface. Those carboxylic groups can be used for further complexation with the drug cisplatin. We show the possibility of loading cisplatin on such nanoparticles and that the loading is dependent on the degree of surface functionalization. The drug release is dependent on time and temperature, making it ideal for applications involving hyperthermia. We show the possibility of applying hyperthermia in vitro using these nanoparticles. When loaded with cisplatin a stronger cytotoxic effect is observed. Such particles could be potentially used as multimodal anti-cancer agents for therapies based on the synergistic effect of chemotherapy and hyperthermia.     

Synthesis and characterization of high strength polyimide/silicon nitride nanocomposites with enhanced thermal and hydrophobic properties

Polyimide (PI) composite films were synthesized incorporating amino modified silicon nitride (Si3N4) nanoparticles into PI matrix via in situ polymerization technique. The mechanical and thermal perfor-mances as well as the hydrophobic properties of the as prepared composite films were investigated with respect to the dosage of the filler in the PI matrix. According to Thermogravimetric (TGA) analysis, mean-ingful improvements were achieved in T5 (5％weight loss temperature) and T10 (10％weight loss temper-ature) up to 54.1 ℃ and 52.4 ℃, respectively when amino functionalized nano-Si3N4 particles were introduced into the PI matrix. The differential scanning calorimetry (DSC) results revealed that the glass transition temperature (Tg) of the composites was considerably enhanced up to 49.7 ℃ when amino func-tionalized Si3N4 nanoparticles were incorporated in the PI matrix. Compared to the neat PI, the PI/Si3N4 nanocomposites exhibited very high improvement in the tensile strength as well as Young's modulus up to 105.4％ and 138.3％, respectively. Compared to the neat PI, the composites demonstrated highly decreased water absorption behavior which showed about 68.1％ enhancement as the content of the nanoparticles was increased to 10 wt％. The SEM (Scanning electron microscope) images confirmed that the enhanced thermal, mechanical and water proof properties are essentially attributed to the improved compatibility of the filler with the matrix and hence, enhanced distribution inside the matrix because of the amino groups on the surface of Si3N4 nanoparticles obtained from surface functionalization.     

Surface functionalization of SBA-15 particles for ibuprofen delivery

We have synthesized SBA-15 particles and functionalized their surface with different functional groups (amine, diamine, and sulfonic acid groups) to use them as carrier materials in drug delivery. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption, and zeta potential measurements were used to characterize the synthesized particles. After surface functionalization, the surface of the sulfonic acid-functionalized particles was more acidic than that of the other particles. Using ibuprofen as a model drug, we found that the release rate increased at higher pH. Furthermore, the particles with the sulfonic acid groups exhibited higher release rate than those with the amine and diamine groups. We explained the difference in the release rate using different electrostatic interaction between drug and particle surface that was caused by the surface functionalization. These results should enable design of drug carrier materials based on the SBA-15 particles with the desired release rate.     

烷基烯酮二聚体对褐煤疏水改性及成浆性能的影响

针对褐煤表面亲水基团丰富、孔隙发达导致煤成浆性能差的问题,以阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）为乳化剂制备了阳离子烷基烯酮二聚体（AKD）乳液,将其涂覆在经微波脱水后的褐煤颗粒表面,使煤样表面获得较强的疏水性;利用比表面积分析仪（BET）、X射线光电子能谱（XPS）和化学滴定法研究了AKD与煤表面的作用机理,同时测定了煤水体系的zeta电位以及煤水界面润湿性,结果表明AKD在煤表面发生了物理化学吸附,并当阳离子AKD乳液用量为1.5%时,改性煤粒表面zeta电位绝对值达到最大,褐煤与水的接触角从50.92°增加到121.10°;再将改性后的褐煤颗粒配合聚萘磺酸盐分散剂制得高浓度的水煤浆,当褐煤水煤浆黏度保持1000mPa·s时,最大成浆浓度从原煤的56.6%增加到61.20%,并且随水煤浆存放时间的延长其水煤浆的黏度保持稳定。     

Wittig-Horner reactions on styrene-divinylbenzene supports with benzaldehyde side-groups

Summary A styrene-divinylbenzene copolymer functionalized with aldehyde was prepared under phase transfer catalyzed (PTC) conditions. A statistical method for the calculation of the degree of functionalization with aldehyde groups is proposed. The degree of functionalization with aldehyde groups is relatively high. Styrene-divinylbenzene polymers functionalized with benzaldehyde groups were used in Wittig-Horner reaction, in order to introduce double bonds on polymers. The reactions were carried out using PTC method, solid-liquid-solid (s-l-s) (K₂CO₃, tetrahydrofuran, tetraethylammonium iodide) system. Phase transfer catalyzed reactions are often more easily and cheaply carried out than conventional method and they are therefore of particular interest.     

Organic functionalization of carbon nanofibers for composite applications

The present work reports the study of the effect of different chemical functionalization methods on the interfacial characteristics of the polymer composites formed. The chemically modified carbon nanofibers were blended with polypropylene (PP) and PP modified with maleic anhydride on a mini twin‐screw extruder. The functionalization methods were designed for minimum fiber damage and enhanced fiber/matrix interactions by chemical reaction of the functional groups introduced at the nanofibers surface with the maleic anhydride grafted at the PP. The degree of nanofiber functionalization was studied using thermogravimetric analysis. The composites were analyzed for nanofiber dispersion, mechanical properties, and electrical resistivity. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis,characterization, and microsphere formation of galactosylated chitosan

Chitosan derivative with galactose groups, which was recognized specifically by the asialoglycoprotein receptor (ASGR), was synthesized by introduction of the galactose group into the amino group of chitosan. The chemical structure of galactosylated chitosan was characterized by FT‐IR, ¹H‐NMR, ¹³C‐NMR, WAXD, and DSC techniques. The results indicated that although acyl reaction on the part of amino groups of chitosan took place, the degree of galactosylated substitution was 20%, and the crystallization, solubility, stability, and other physical properties were different from chitosan. Microspheres of chitosan and galactosylated chitosan were prepared by the physical precipitation and coacervation method with sodium sulfate, respectively. The characterizations of microspheres were determined by means of scanning electron microscopy (SEM), particle size/ζ potential analysis, and DSC methods. Spherical, positively charged chitosan and galactosylated chitosan microspheres were formed, with an average diameter of 0.54 and 1.05 μm, and average ζ potential of +17 mV and +15 mV, respectively. The novel galactosylated chitosan microspheres may be used as a potential drug delivery system with passive and active hepatic targeting properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 659–665, 2004