Jui Che Lin

Surface properties and hemocompatibility of alkyl-siloxane monolayers supported on silicone rubber: effect of alkyl chain length and ionic functionality

Self-assembled monolayers of alkylsiloxanes supported on poly(dimethylsiloxane) (PDMS) rubber were used as model systems to study the relation between blood compatibility and surface composition. The inner lumen of PDMS tubes were first treated with an oxygen plasma. The resultant oxidized surfaces were post-derivatized by reaction with alkyltrichlorosilanes to form the monolayer films. The alkyl chain lengths used were slightly longer than in a previous study, and this may alter the phase-state of the monolayer from liquid-like to crystalline. The chemical properties of the monolayer were controlled by varying the chemical composition of the alkyltrichlorosilanes used. Terminal functionalities included -CH3, -CF3, -COOH, -SO3H and -(CH2CH2O)4OH. Surface derivatization was verified with static contact angle measurements and X-ray photoelectron spectroscopy. Blood compatibility was evaluated using a canine ex vivo arterio-venous series shunt model. Surfaces grafted with hydrophobic head groups such as -CH3 and -CF3 were significantly less thrombogenic than the surfaces composed of ionic head groups such as -COOH and -SO3H. Surfaces enriched in -(CH2CH2O)4OH had an intermediate thrombogenicity. Silastic pump grade tubing and polyethylene tubing, used as controls, were found to be the least thrombogenic of all the surfaces tested.

In vitro feasibility study of the use of a magnetic electrospun chitosan nanofiber composite for hyperthermia treatment of tumor cells

Hyperthermia has been reported to be an effective cancer treatment modality, as tumor cells are more temperature-sensitive than their normal counterparts. Since the ambient temperature can be increased by placing magnetic nanoparticles in an alternating magnetic field it has become of interest to incorporate these magnetic nanoparticles into biodegradable nanofibers for possible endoscopic hyperthermia treatment of malignant tumors. In this preliminary investigation we have explored various characteristics of biodegradable electrospun chitosan nanofibers containing magnetic nanoparticles prepared by different methods. These methods included: (1) E-CHS-Fe(3)O(4), with electrospun chitosan nanofibers directly immersed in a magnetic nanoparticle solution; (2) E-CHS-Fe(2+), with the electrospun chitosan nanofibers initially immersed in Fe(+2)/Fe(+3) solution, followed by chemical co-precipitation of the magnetic nanoparticles. The morphology and crystalline phase of the magnetic electrospun nanofiber matrices were determined by scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray diffraction spectroscopy. The magnetic characteristics were measured using a superconducting quantum interference device. The heating properties of these magnetic electrospun nanofiber matrices in an alternating magnetic field were investigated at a frequency of 750 kHz and magnetic intensity of 6.4 kW. In vitro cell incubation experiments indicated that these magnetic electrospun nanofiber matrices are non-cytotoxic and can effectively reduce tumor cell proliferation upon application of a magnetic field.

Synthesis, surface characterization, and platelet reactivity evaluation for the self-assembled monolayer of alkanethiol with sulfonic acid functionality

Owing to the capability of fabricating a well-defined chemical structure on the surface, self-assembled alkanethiols with a variety of terminal functionalities were prepared on the gold substrate for investigating the interactions between the biological environment and synthetic surface. In this study, we report the synthesis of the sulfonic acid terminated long-chain alkanethiol, 10-mercaptodecane-sulfonic acid, for direct preparation of a self-assembled monolayer (SAM) with -SO(3)H functionality. Nuclear magnetic resonance (NMR) and elemental analysis studies indicated that a high purity of sulfonic acid terminated alkanethiol was obtained. Surface characterization results showed that the -SO(3)H terminated SAM is hydrophilic and has a slightly higher hysteresis value, possibly because of the slower chain mobility of the bound sulfonic acid alkanethiol. Electron spectroscopy for chemical analysis (ESCA) analysis demonstrated that the -SO(3)H terminal group is situated in the outermost layer of the monolayer, as previous alkanethiol SAM structure models proposed. The platelet reactivity of the -SO(3)H SAM was higher than that of -OH SAM but less than the -CH(3) terminated one in vitro, whereas similar platelet reactivity was noticed between the -SO(3)H and -COOH SAMs. The higher platelet reactivity found on the -SO(3)H SAM could be caused by the higher surface functional group density inherent in the SAM structure and/or the composition and conformation state of the adsorbed protein layer.

Surface characterization and platelet adhesion studies of self-assembled monolayer with phosphonate ester and phosphonic acid functionalities

Because of its well-defined surface configuration and creative chemical structure, an alkanethiol self-assembled monolayer (SAM) on gold is a model surface for a blood compatibility investigation. In this study two laboratory-synthesized long-chain alkanethiols, HS(CH(2))(10)PO(3)-(C(2)H(5))(2) and HS(CH(2))(10)PO(3)H(2), were employed for the direct preparation of SAMs with nonionic and ionic functional groups. Various instrumental analyses confirmed the high purity of the phosphonate ester and phosphonic acid terminated alkanethiols. The surface characterization results showed the -PO(3)H(2) terminated SAM was more hydrophilic than the -PO(3)(C(2)H(5))(2) one. Higher hysteresis values for the -PO(3)(C(2)H(5))(2) and -PO(3)H(2) terminated SAMs were noted, which were possibly due to the steric hindrance of the bulky terminal groups. In addition, the O(2) plasma + EtOH-rinse pretreated Au sample was hydrophilic because of the residual gold oxide on the surface. This finding was supported by electron spectroscopy for chemical analysis (ESCA) as well. The ESCA analysis also indicated bulky and polar terminal groups [-PO(3)(C(2)H(5))(2) and -PO(3)H(2)] were situated in the outermost layer of its monolayer. The platelet reactivity on the SAM with the nonionic group -PO(3)(C(2)H(5))(2) was less than those of the ionic terminated SAMs -COOH and -PO(3)H(2). The O(2) plasma + EtOH-rinse pretreated gold substrate exhibited the least platelet-activating surface among the different pretreated Au substrates studied.

Cometabolic degradation kinetics of TCE and phenol by Pseudomonas putida

Modeling of cometabolic kinetics is important for better understanding of degradation reaction and in situ application of bio-remediation. In this study, a model incorporated cell growth and decay, loss of transformation activity, competitive inhibition between growth substrate and non-growth substrate and self-inhibition of non-growth substrate was proposed to simulate the degradation kinetics of phenol and trichloroethylene (TCE) by Pseudomonas putida. All the intrinsic parameters employed in this study were measured independently, and were then used for predicting the batch experimental data. The model predictions conformed well to the observed data at different phenol and TCE concentrations. At low TCE concentrations (<2 mg l(-1)), the models with or without self-inhibition of non-growth substrate both simulated the experimental data well. However, at higher TCE concentrations (>6 mg l(-1)), only the model considering self-inhibition can describe the experimental data, suggesting that a self-inhibition of TCE was present in the system. The proposed model was also employed in predicting the experimental data conducted in a repeated batch reactor, and good agreements were observed between model predictions and experimental data. The results also indicated that the biomass loss in the degradation of TCE below 2 mg l(-1) can be totally recovered in the absence of TCE for the next cycle, and it could be used for the next batch experiment for the degradation of phenol and TCE. However, for higher concentration of TCE (>6 mg l(-1)), the recovery of biomass may not be as good as that at lower TCE concentrations.

Water-based synthesis and processing of novel biodegradable elastomers for medical applications

Biodegradable elastomers in the form of polyurethane nanoparticles (NPs) were successfully synthesized based on the combinations of two hydrolysis-prone polyester diols by a green water-based process. The anionic nature of the polymers successfully rendered polyurethane NPs (30-50 nm) consisting of approximately 200-300 polymer chains. The mechanical properties and degradation rate could be adjusted by the types and ratios of the component oligodiols in the soft segment. We demonstrated the feasibility using these biodegradable NPs as building blocks to generate self-assembled morphologies in nanometric, micrometric, or bulk scale, bearing excellent elasticity and biocompatibility. The elastic NPs and their various assembled forms represent a series of smart biodegradable elastomers with potential medical applications.

Surface characterization and platelet adhesion studies on polyurethane surface immobilized with C60

Due to its distinctive molecular configuration, C60 and its derivatives have been the research focus in exploring its electrical, mechanical, optical, and even biological applications during the past decades. In this investigation, C60 molecules are grafted onto the polyurethane surface, which is pretreated with oxygen plasma activation, through amine-terminated silane coupling agents. ESCA analysis indicates that the C60 molecules spontaneously grafted onto the amine-terminated PU substrate through nucleophilic additions to the fullerene double bonds which fuse two six-membered rings. More amine functional groups are formed on the PU surface if 4-aminobutyldimethylmethoxysilane is used as the coupling agent. In vitro platelet adhesion assay shows the C60 grafted PU are more platelets activating than the nontreated PU control. This might be attributed to the synergistic effect of the grafted C60 molecules and the few residual amine functional groups which are left after the C60 grafting reaction. Further applications using these C60 grafted polyurethane surfaces as the cell adhesion and cell growth substrates are currently under exploration.

Studies of a novel human thrombomodulin immobilized substrate: Surface characterization and anticoagulation activity evaluation

Immobilization of the anticoagulative or antithrombogenic biomolecule has been considered as one of the important methods to improve the blood compatibility of artificial biomaterials. In this study, a novel immobilization reaction scheme was utilized to incorporate the human thrombomodulin, an endothelial cell associated glycoprotein, onto the cover glass surface with an aim to develop an anticoagulative substrate. Trichlorotriazine and amino-terminated silane were employed as the coupling agents, while the polyethylene glycol with a molecular weight of 1500 was used as the spacer in this reaction scheme. Protein C activation assay indicated the immobilized human thrombomodulin still has this coenzymatic activity but is lower, possibly due to the conformation variation by the coupling agents. In vitro platelet adhesion assay has demonstrated the surface with immobilized human thrombomodulin is much less platelet-activating than others. Therefore, the novel reaction scheme proposed here is very promising for future development of an anticoagulative silicon or cover glass substrate (e.g. implantable sensor or biochip) by the immobilization of antithrombogenic protein, such as the human thrombomodulin in this study.

Surface characterization and in vitro platelet compatibility study of surface sulfonated chitosan membrane with amino group protection-deprotection strategy

Glycosaminoglycans (GAGs) are the main components of the extracellular matrix (ECM). Studies have indicated that scaffolds modified by GAGs could improve cell proliferation and differentiation. Chitosan, the second-most abundant nature polysaccharide, has a structure similar to that of GAGs. Due to its relatively lower cost as compared to GAGs, many researchers have tried to incorporate sulfonate or carboxyl groups into the chitosan structure with the aim to form a GAG-like structure. However, these modifications were carried out on the reactive amino groups that were thought as the major character, resulting in special biological properties associated with chitosan. Such a decrease of amino-functional group density would very likely alter the specific biological properties of chitosan. Therefore, an amino group protection–deprotection strategy was explored in this study for surface sulfonation of chitosan membrane with the aim to imitate GAG structures. Various surface chemical characterization results, as well as surface zeta potential measurements have indicated that both sulfonate/sulfonic and amino functionalities were coexistent on the deprotected sulfonated chitosan specimen. In vitro platelet adhesion testing has shown that such a deprotected sulfonated chitosan membrane can increase the amount of platelet adhesion while keep those adhered remained unactivated. At the same time the presence of deprotected sulfonated chitosan film extended the plasma recalcification time value. With this protection–deprotection strategy, a further chemical grafting of bioactive molecules, such as RGD peptide, using the recovered amino functionalities, can be pursued on these sulfonated chitosan specimens.

Surface characterization and platelet compatibility evaluation of surface-sulfonated chitosan membrane

The effect of various sulfonated derivatives of chitosan on platelet activation and blood coagulation was examined. The surface properties of artificial biomaterials have been thought as the key factors which mediate the interactions between the biological environment and biomaterial itself. In this study, the sulfonation was directly performed on the chitosan membrane surface. The chitosan membrane was surface-sulfonated by reactions with sulfur-pyridine trioxide complex (SO3/pyridine) in H2O solution and N,N-sulfur-dimethylformamide trioxide complex (SO3/DMF) in DMF.Blood compatibility was evaluated by an in vitro platelet adhesion assay. The surface reaction of SO3/pyridine in aqueous acid medium yields N,O-sulfated chitosan with cationic NH+ 3 groups. After neutralization, this surface has been shown to induce a low degree of platelet adhesion and activation. When the surface-sulfonation is performed in an aqueous alkaline medium, although the degree of sulfonation is lower than the samples above, the N-sulfated chitosan significantly reduced the adhesion and activation of platelets. For the acidic SO3/DMF reaction system, N,O-sulfated chitosan was obtained with a high extent of sulfonation and cationic NH3+groups. On this surface fully spread platelets and some platelet aggregates were found instead. This may be attributed to the ionic interactions between the platelets membrane surface and the cationic groups on the modified chitosan membrane.