Shape-memory surfaces with on-demand, tunable nanopatterns are developed to observe time dependent changes in cell alignment using temperature-responsive poly(ϵ-caprolactone) (PCL) films. Temporary grooved nanopatterns are easily programmed on the films and triggered to transition quickly to permanent surface patterns by the application of body heat. A time-dependent cytoskeleton remodeling is also observed under biologically relevant conditions.
We propose a new approach to fabricate reversible self-bending actuators utilizing a photo-triggered pH jump reaction. A photo-initiated proton-releasing agent of o-nitrobenzaldehyde (NBA) was successfully integrated into bilayer hydrogels composed of a polyacid layer, poly(Nisopropylacrylamide-co-2-carboxyisopropylacrylamide) (P(NIPAAm-co-CIPAAm)) and a polybase layer, poly(N-isopropylacrylamide-co-N,N 0 -dimethylaminopropylacylamide) (P(NIPAAm-co-DMAPAAm)), where the adhesion of both layers was achieved via electrophoresis of semiinterpenetrating polyelectrolyte chains. The NBA-integrated bilayer gels demonstrated quick proton release upon UV irradiation, allowing the pH within the gel to decrease below the volume phase transition pH in 30 seconds. By controlling the NBA concentration and the gel thickness, the degrees and the kinetics of bending were easily controlled. Reversible bending was also studied with respect to the NBA concentration in response to 'on-off' UV irradiation. Additionally, self-bending of the non-UV irradiated region of the gel was also achieved because the generated protons gradually diffused toward the non-irradiated region. The proposed system can be potentially applied in the fields of mechanical actuators, controlled encapsulation and drug release, robotics and microfluidic technologies because control over autonomous motion by both physical and chemical signals is essential as a programmable system for real biomedical and nano-technological applications.
Poly(N-isopropylacrylamide) (PIPAAm) of controlled molecular weight was densely grafted onto glass capillary lumenal surfaces using surface-initiated atom transfer radical polymerization (ATRP). Temperature-dependent changes of these thermoresponsive brush surfaces with hydrophobic steroids were investigated by exploiting thermoresponsive aqueous wettability changes of the polymer-modified surfaces in microfluidic systems. IPAAm was polymerized on ATRP initiator-immobilized glass surfaces using CuCl/CuCl(2)/tris(dimethylaminoethyl)amine (Me(6)TREN) as an ATRP catalyst in water at 25 degrees C. PIPAAm graft layer thickness and its homogeneity on glass surfaces are controlled by changing ATRP reaction time. Aqueous wettability changes of PIPAAm-grafted surfaces responses drastically changed to both grafted polymer layer thickness and temperature, especially at lower temperatures. Temperature-responsive surface properties of these PIPAAm brushes within capillary inner wall surfaces were then investigated using capillary chromatography. Effective interaction of hydrophobic steroids with dehydrated, hydrophobized PIPAAm-grafted capillary surfaces was observed above 30 degrees C without any column packing materials. Steroid elution behavior from PIPAAm-grafted capillaries contrasted sharply with that from PIPAAm hydrogel-grafted porous monolithic silica capillaries prepared by electron beam (EB) irradiation wherein significant peak broadening was observed at high-temperature regardless of sample hydrophobicity factors (log P values), indicating multistep separation modes in coated monolithic silica capillaries. In conclusion, thermoresponsive polymer-grafted capillary inner wall surfaces prepared by ATRP exhibit useful temperature-dependent surface property alterations effective to regulate interactions with biomolecules without requirements for separation bed packing materials within the capillary lumen.
Thermally regulated flow control using a thermoresponsive polymer grafted onto surfaces of capillary lumen facilitates rapid, reliable, and repeatable open–close cycles (see Figure). Hydration of the grafted polymer chains on the internal surfaces may increase the microviscosity of the hydration layers at the wall interfaces without physically occluding the lumen, producing complete and reversible on/off flow valving in microchannels under hydrostatic pressures relevant for microfluidics approaches.
Here we present on-demand switchable microchip materials that display potent rewritable and shapememory properties which are shown to contribute to fluidic control as pumps and valves. Semicrystalline poly(3-caprolactone) (PCL) was chemically crosslinked to show shape-memory effects over its melting temperature (T m ) because the crosslinking points set the permanent shape and the crystalline domains serve as thermally reversible mobile phase. The T m was adjusted to nearly biologically relevant temperatures by crosslinking two and four branched PCL macromonomers with different ratios. The T m decreased proportionally with increasing four branched PCL content because an increase in crosslinking density imposes restrictions on chain mobility and reduces the crystallization. The sample with 50/50 wt % mixing ratio of two-and four-PCL had a T m around 33 C. Permanent surface patterns were first generated by crosslinking the macromonomers in a mold, and temporary surface patterns were then embossed onto the permanent patterns. From the cross-sectional profiles, almost 100% recovery of the permanent pattern was successfully achieved after shape-memory transition. The effects of dynamic geometric changes of the shape-memory channels on the microfluidic flow were also investigated and shape-memory channel closing was achieved by the application of heat. The proposed system can be potentially applied as a new class of microfluidic control techniques, which enables portable microfluidic based diagnostic tools for biomedical applications and environmental monitoring allowing on-site analysis.
The following errors are hereby corrected in the article above: (1) In the table of contents entry, and on the 9th line of the 2nd paragraph in the 2nd column on page 3343, "2.0 × 10 8 S/m" is replaced with "2.0 × 10 7 S/m". (2) Figure 2b is replaced with the Figure shown here: These errors do not affect the scientifi c conclusions of the original article. The authors apologize for any inconvenience that may have been caused due to these errors.
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