We developed a confocal Raman microspectroscopy system combined with a laser trapping technique and applied it to aqueous solutions (H(2)O and D(2)O) of poly(N-isopropylacrylamide) (PNIPA), which is well-known as a representative thermo-responsive polymer, i.e., phase transition/separation between coiled and globular states. By introducing a near-infrared (1064 nm) laser beam into a microscope, PNIPA microparticles were produced at the focused spot of the laser beam, both in H(2)O and D(2)O. By using the present system, we succeeded in obtaining the Raman spectra of PNIPA in the coiled and globular states over a wide wavenumber region (800-3500 cm(-1)) for the first time. For the D(2)O solutions (in which the photothermal effect is negligible and hence the microparticles should be produced purely by the effect of radiation pressure), some significant differences were observed in the Raman spectra for the coiled state, in the globular state, and for laser induced microparticles. By analyzing these spectra in detail, we revealed that the structure of the laser-induced microparticles was analogous to that in the globular state. We also discuss the fundamental mechanism underlying the transformation of the higher order structure of a polymer by radiation pressure.
A survey was prepared of 136 cases of laparotomy in patients with Behçet's disease and intestinal ulcers in Japan. The incidence of the disease is highest in males in the fourth and fifth decades. The ulcers are frequently found in the terminal ileum and the cecum. The ulcers are liable to perforate into the abdominal cavity, so that many patients require emergency operation. Resection of the ileocecal region or right half of the colon is the usual operation in the treatment of this disease. However, it is necessary to search for skip lesions, because multiple ulcers may be present. The incidence of postoperative complications and postoperative recurrence of ulcers is so high that supplementary management is often required.
We demonstrate that phase separation of an aqueous poly(vinyl methyl ether) (PVME) solution can be triggered not only by a temperature change but also by photon pressure. A near-infrared continuous wave laser beam (λ=1064 nm) was focused through an objective lens into a heavy water (D2O) solution of PVME. A single PVME microparticle was produced and trapped at the focal point of the laser beam within several hundreds of seconds after switching on the laser. The origin of the microparticle formation (phase separation) is ascribed essentially to the photon force of the laser beam, and not to a rise in the local temperature, since heavy water is transparent at 1064 nm. The structures of the PVME microparticles produced by laser irradiation were studied in detail using confocal Raman microspectroscopy. Raman spectra of the microparticles and coiled/globular PVME were observed successfully over a wide wavenumber region. It was confirmed that the phase transition of the polymer chains from coiled to globular states proceeded during microparticle formation. The fundamental mechanism of photo-induced phase separation of PVME is discussed in terms of the interactions between the polymer and the photon force.
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