Modeling the Kinetics, Curing Depth, and Efficacy of Radical-Mediated Photopolymerization: The Role of Oxygen Inhibition, Viscosity, and Dynamic Light Intensity.

Kinetic equations for a modeling system with type-I radical-mediated and type-II oxygen-mediated pathways are derived and numerically solved for the photopolymerization efficacy and curing depth, under the quasi-steady state assumption, and bimolecular termination. We show that photopolymerization efficacy is an increasing function of photosensitizer (PS) concentration (C 0) and the light dose at transient state, but it is a decreasing function of the light intensity, scaled by [C 0/I 0]0.5 at steady state. The curing (or cross-link) depth is an increasing function of C 0 and light dose (time × intensity), but it is a decreasing function of the oxygen concentration, viscosity effect, and oxygen external supply rate. Higher intensity results in a faster depletion of PS and oxygen. For optically thick polymers (>100 um), light intensity is an increasing function of time due to PS depletion, which cannot be neglected. With oxygen inhibition effect, the efficacy temporal profile has an induction time defined by the oxygen depletion rate. Efficacy is also an increasing function of the effective rate constant, K = k'/ k T 0 . 5 , defined by the radical producing rate (k') and the bimolecular termination rate (k T). In conclusion, the curing depth has a non-linear dependence on the PS concentration, light intensity, and dose and a decreasing function of the oxygen inhibition effect. Efficacy is scaled by [C 0/I 0]0.5 at steady state. Analytic formulas for the efficacy and curing depth are derived, for the first time, and utilized to analyze the measured pillar height in microfabrication. Finally, various strategies for improved efficacy and curing depth are discussed.

Dual-Wavelength (UV and Blue) Controlled Photopolymerization Confinement for 3D-Printing: Modeling and Analysis of Measurements.

The kinetics and modeling of dual-wavelength (UV and blue) controlled photopolymerization confinement (PC) are presented and measured data are analyzed by analytic formulas and numerical data. The UV-light initiated inhibition effect is strongly monomer-dependent due to different C=C bond rate constants and conversion efficacies. Without the UV-light, for a given blue-light intensity, higher initiator concentration (C10) and rate constant (k') lead to higher conversion, as also predicted by analytic formulas, in which the total conversion rate (RT) is an increasing function of C1 and k'R, which is proportional to k'[gB1C1]0.5. However, the coupling factor B1 plays a different role that higher B1 leads to higher conversion only in the transient regime; whereas higher B1 leads to lower steady-state conversion. For a fixed initiator concentration C10, higher inhibitor concentration (C20) leads to lower conversion due to a stronger inhibition effect. However, same conversion reduction was found for the same H-factor defined by H0 = [b1C10 - b2C20]. Conversion of blue-only are much higher than that of UV-only and UV-blue combined, in which high C20 results a strong reduction of blue-only-conversion, such that the UV-light serves as the turn-off (trigger) mechanism for the purpose of spatial confirmation within the overlap area of UV and blue light. For example, UV-light controlled methacrylate conversion of a glycidyl dimethacrylate resin is formulated with a tertiary amine co-initiator, and butyl nitrite. The system is subject to a continuous exposure of a blue light, but an on-off exposure of a UV-light. Finally, we developed a theoretical new finding for the criterion of a good material/candidate governed by a double ratio of light-intensity and concentration, [I20C20]/[I10C10].

Thiol-Ene Photopolymerization: Scaling Law and Analytical Formulas for Conversion Based on Kinetic Rate and Thiol-Ene Molar Ratio.

Kinetics and analytical formulas for radical-mediated thiol-ene photopolymerization were developed in this paper. The conversion efficacy of thiol-ene systems was studied for various propagation to chain transfer kinetic rate-ratio (RK), and thiol-ene concentration molar-ratio (RC). Numerical data were analyzed using analytical formulas and compared with the experimental data. We demonstrated that our model for a thiol-acrylate system with homopolymerization effects, and for a thiol-norbornene system with viscosity effects, fit much better with the measured data than a previous model excluding these effects. The general features for the roles of RK and RC on the conversion efficacy of thiol (CT) and ene (CV) are: (i) for RK = 1, CV and CT have the same temporal profiles, but have a reversed dependence on RC; (ii) for RK >> 1, CT are almost independent of RC; (iii) for RK << 1, CV and CT have the same profiles and both are decreasing functions of the homopolymerization effects defined by kCV; (iv) viscosity does not affect the efficacy in the case of RK >> 1, but reduces the efficacy of CV for other values of RK. For a fixed light dose, higher light intensity has a higher transient efficacy but a lower steady-state conversion, resulting from a bimolecular termination. In contrast, in type II unimolecular termination, the conversion is mainly governed by the light dose rather than its intensity. For optically thick polymers, the light intensity increases with time due to photoinitiator depletion, and thus the assumption of constant photoinitiator concentration (as in most previous models) suffers an error of 5% to 20% (underestimated) of the crosslink depth and the efficacy. Scaling law for the overall reaction order, defined by [A]m[B]n and governed by the types of ene and the rate ratio is discussed herein. The dual ratio (RK and RC) for various binary functional groups (thiol-vinyl, thiol-acrylate, and thiol-norbornene) may be tailored to minimize side effects for maximal monomer conversion or tunable degree of crosslinking.

Modeling the Optimal Conditions for Improved Efficacy and Crosslink Depth of Photo-Initiated Polymerization.

Optimal conditions for maximum efficacy of photoinitiated polymerization are theoretically presented. Analytic formulas are shown for the crosslink time, crosslink depth, and efficacy function. The roles of photoinitiator (PI) concentration, diffusion depth, and light intensity on the polymerization spatial and temporal profiles are presented for both uniform and non-uniform cases. For the type I mechanism, higher intensity may accelerate the polymer action process, but it suffers a lower steady-state efficacy. This may be overcome by a controlled re-supply of PI concentration during the light exposure. In challenging the conventional Beer⁻Lambert law (BLL), a generalized, time-dependent BLL (a Lin-law) is derived. This study, for the first time, presents analytic formulas for curing depth and crosslink time without the assumption of thin-film or spatial average. Various optimal conditions are developed for maximum efficacy based on a numerically-fit A-factor. Experimental data are analyzed for the role of PI concentration and light intensity on the gelation (crosslink) time and efficacy.

Continuous lipid extraction of microalgae using high-pressure carbon dioxide.

Sequestering carbon, purifying water, and creating biofuel materials using microalgae are of global interest in the R&D field. However, extracting algal oil consumes a high amount of energy, which is an obstacle for the biofuel market. Nontoxic and recyclable high-pressure CO2 extraction processes are being developed by numerous researchers; however, most of these processes use batch operations mixed with a large amount of co-solvent and require improvement. We fabricated a continuous high-pressure CO2 extraction system, evaluating the optimal parameters for the extraction process. The various parameter tests included temperature, pressure, pretreatment methods, ratio, and the species of co-solvent. We integrated the optimal parameters from previous tests, using a 5-d continuous operation. Compared with traditional solvent extraction, a 90.56% extraction yield ratio was achieved using this continuous extraction method. This shows the stable, high extraction yields of this continuous high-pressure CO2 extraction system.

Laser-induced carotid artery injury model in the rat for therapeutic agent screening.

The aims of this study were to establish a rat model of carotid artery injury and to evaluate its suitability for evaluating therapeutic agents active against endothelial proliferation. Wistar-Kyoto rats were injected intravenously with the photochemically reactive dyes rose bengal or Evans blue, and the carotid artery was then focally irradiated with laser light of the appropriate wavelength. Histological sections of the carotid artery were analyzed to determine the appropriate parameters for this model. Ferulic acid was used to assess the suitability of this model for drug screening. No animal died as a result of the photochemical treatment. Endothelial proliferation in the carotid artery was observed in rats injected with rose Bengal and exposed to green laser light. Ferulic acid (400 mg/kg per day) significantly (p<0.05) reduced endothelial proliferation in the carotid artery 28 days after injury in dye-treated animals compared with vehicle-treated animals. This simple experimental rat model is suitable for studying factors inhibiting endothelial thickening after vessel damage and for developing therapeutic strategies active against endothelial proliferation.

Assessment of mouse hind limb endothelial function by measuring femoral artery blood flow responses.

OBJECTIVE: Substantial progress has been made in cell therapy strategies and in gene- and cytokine-introduced angiogenesis using a variety of mouse models, such as hind limb ischemia models. Endothelial function is an important target in evaluating the effects and outcomes of these potential therapies. Although animal models have been established for estimating endothelium-dependent function by measuring the blood flow responses in carotid and renal arteries and the abdominal aorta, a model specific for an indicated hind limb by measuring femoral artery blood flow (FABF) has not yet been established. METHODS: A 2-day protocol was designed, including exploration of the segmental femoral artery on the first day, and evaluation of endothelium-dependent vasodilatation function the next day. By placing a transonic flow probe around the left femoral artery, the FABF in response to endothelium-dependent and endothelium-independent vasodilatory stimulations was reproducibly measured. Hemodynamic measurements, including the left FABF and mean arterial pressure, were recorded. RESULTS: In normal controls, the baseline left FABF averaged 0.12 ± 0.01 mL/min. Acetylcholine increased the FABF up to 0.41 ± 0.02 mL/min. Rose bengal-associated photochemical injury was titrated to cause endothelial dysfunction but without disturbing the integrity of the endothelial layer. The response to acetylcholine significantly decreased 10 minutes after photochemical injury and was further impaired after 1 and 24 hours. However, the response to nitroprusside was preserved. A femoral and iliac artery wire-injury model was also introduced to cause endothelial and smooth muscle cell injury. One day after the wire injury, the responses to acetylcholine and nitroprusside injections were both remarkably attenuated. CONCLUSIONS: This model can be widely used to analyze the in vivo endothelium-dependent vasodilatation function before and after a variety of therapeutic interventions on a mouse hind limb.

Effects of natto extract on endothelial injury in a rat model.

Vascular endothelial damage has been found to be associated with thrombus formation, which is considered to be a risk factor for cardiovascular disease. A diet of natto leads to a low prevalence of cardiovascular disease. The aim of the present study was to investigate the effects of natto extract on vascular endothelia damage with exposure to laser irradiation. Endothelial damage both in vitro and in vivo was induced by irradiation of rose bengal using a DPSS green laser. Cell viability was determined by MTS assay, and the intimal thickening was verified by a histological approach. The antioxidant content of natto extract was determined for the free radical scavenging activity. Endothelial cells were injured in the presence of rose bengal irradiated in a dose-dependent manner. Natto extract exhibits high levels of antioxidant activity compared with purified natto kinase. Apoptosis of laser-injured endothelial cells was significantly reduced in the presence of natto extract. Both the natto extract and natto kinase suppressed intimal thickening in rats with endothelial injury. The present findings suggest that natto extract suppresses vessel thickening as a synergic effect attributed to its antioxidant and anti-apoptosis properties.