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Highlights • It is difficult to irradiate individual mouse lymph nodes (LNs) 1–2 mm in diameter. • A maximum single dose is, Utilizing mice with swollen lymph nodes, we succeeded in irradiating individual metastatic lymph nodes through a hole in a lead shield. This system enabled us to increase the radiation dose to >8 Gy (the lethal dose for total-body irradiation) and evaluate both direct and abscopal antitumor effects.

A perfusion defect in metastatic lymph nodes (LNs) can be visualized as a localized area of low contrast on contrast-enhanced CT, MRI or ultrasound images. Hypotheses for perfusion defect include abnormal hemodynamics in neovascular vessels and decrease in blood flow in pre-existing blood vessels in the parenchyma due to compression of tumor growth in the LNs. However, the mechanism of perfusion defects in LNs during the early stage of LN metastasis has not yet been investigated. Here we show that the formation of a tumor mass with very few microvessels was associated with the development of a perfusion defect in the non-enlarged LN at the early stage of LN metastasis. We found in a mouse model of LN metastasis induced using non-keratinizing tumor cells that during formation of the perfusion defect in non-enlarged LN, the number of blood vessels £ 50 mm in diameter decreased, while the volume of existing blood vessels >50 mm in diameter increased using contrast-enhanced high-frequency ultrasound and contrast-enhanced micro-CT imaging systems with a maximum spatial resolution of > 30 mm. Furthermore, we found that tumor angiogenesis and pO2 changes in the metastatic LN were not observed. Our results demonstrate that the perfusion defect appear to be a specific form of tumorigenesis in the LN as vascular-rich organ at the early stage of metastasis. We anticipate a perfusion defect on ultrasound, CT or MRI images to be used as an indicator in the non-enlarged LN at the early stage of LN metastasis.

This study demonstrates the facile preparation of poly(N-isopropylacrylamide) (PNIPAM)-immobilized Petri dishes by drop-casting a star-shaped copolymer of hyperbranched polystyrene (HBPS) possessing PNIPAM arms (HBPS-g-PNIPAM) functionalized with polar groups. HBPS was synthesized via reversible addition窶吐ragmentation chain transfer (RAFT) self-condensing vinyl polymerization (SCVP), and HBPS polymers with different terminal structures were prepared by changing the monomer structure. HBPS-g-PNIPAM was synthesized by the grafting of PNIPAM from each terminal of HBPS. To tune the cell adhesion and detachment properties, polar functional groups such as carboxylic acid and dimethylamino groups were introduced to HBPS-g-PNIPAM. Based on surface characterization using scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), and contact angle measurements, the advantage of the hyperbranched structure for the PNIPAM immobilization was evident in terms of the uniformity, stability, and thermoresponsiveness. Successful cell sheet harvesting was demonstrated on dishes coated with HBPS-g-PNIPAM. In addition, the cell adhesion and detachment properties could be tuned by the introduction of polar functional groups.

Interface manipulation to pursue unusual nanostructures was performed using a strategically designed triblock terpolymer with a short middle segment, poly(styrene-b-methyl methacrylate-b-2,2,2-trifluoroethyl methacrylate). A short middle segment of poly(methyl methacrylate) (PMMA) that does not form any distinct domains was found to play an important role in manipulating the interface between the polystyrene (PS) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) domains and forming unconventional partially continuous oblate cylinders with an oblique lattice, as confirmed by small angle X-ray scattering (SAXS) and dual-axis transmission electron microtomography (TEMT). Interface manipulation to pursue unusual nanostructures was performed using a strategically designed triblock terpolymer with a short middle segment, poly(styrene-b-methyl methacrylate-b-2,2,2-trifluoroethyl methacrylate). A short middle segment of poly(methyl methacrylate) (PMMA) that does not form any distinct domains was found to play an important role in manipulating the interface between the polystyrene (PS) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) domains and forming unconventional partially continuous oblate cylinders with an oblique lattice, as confirmed by small angle X-ray scattering (SAXS) and dual-axis transmission electron microtomography (TEMT).

Well-defined double liquid crystalline side-chain type block copolymers (DLC-BCPs) were synthesized by nitroxide-mediated living free radical polymerization (NMP) of two different types of styrene monomers containing liquid crystalline moieties. The molecular weights and compositions were controlled by changing the polymerization time and/or the feed amount of the monomers. The bulk morphologies were studied using wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). DLC-BCPs were favored to form microphase-separated lamellar structures over a wide range of volume fractions. By controlling the annealing conditions, further higher-ordered hierarchical nanostructures were obtained with a long-range alignment, in which the semi-crystalline side-chains were oriented parallel to the interface of microphase-separated lamellar structure. Thin film morphology was investigated using atomic force micrography (AFM). The formation of lamellar nanostructure with a long-range alignment vertically oriented to the silicon wafer substrate was achieved by simple thermal annealing.

Hyperbranched poly(ether sulfone) polymers having sulfonyl chloride end-groups is blended at up to 30 w% with linear poly(ether ether ether sulfone)s and a two-phase system is generated via spinodal decomposition upon drying from a DMAc solution. Conversion of the end-groups from sulfonyl chloride to sulfonic acid is accomplished using 16 M H 2 SO 4 that is also believed to introduce additional sulfonic acid groups at the interface of the linear polymer. The blend films before and after conversion to sulfonic acid have similar tensile strengths as films composed of solely linear polymer (yield stress >40 MPa and Young's modulus >3 GPa m). These films are designed to test the viability of hyperbranched polymers as fuel cell membranes. Proton conductivities of up to 0.03 S cm −1 are observed at 80 °C and 90% R.H indicating a good potential for use of hyperbranched polymers as a proton conduction material.

Triethoxysilyl functionalized hyperbranched polsiloxysilanes at the focal (FT-HBPSs) and terminal (TT-HBPSs) positions were synthesized to investigate adsorption behavior onto a silicon wafer surface. The surface of the silicon wafer adsorbed with the HBPSs was characterized by X-ray photoelectron spectroscopy, atomic force microscopy (AFM), static and dynamic water contact angle measurements. The AFM images indicated the formation size of dot-like structures were approximately 200 nm. The presence of vinyl terminal groups of FT-HBPSs permitted conversion of the surface from a non-polar hydrocarbon to a polar hydroxylated or carboxylated structures. After the polarity was changed, the surface properties were also studied using the above surface analysis techniques. The dynamic contact angle measurement indicated that the silicon wafer surface modified by FT-HBPSs was more hydrophilic in water than TT-HBPS. This behavior can be explained by the difference of connecting points between HBPS and the silicon wafer surface.

Hypoxia appears to have an important role in pathological conditions in many organs such as kidney; however, a method to quantify intracellular oxygen tension in vivo has not been well established. In this study, we established an optical method to quantify oxygen tension in mice kidneys using a cationic lipophilic phosphorescence probe, BTPDM1, which has an intracellular oxygen concentration-sensitive phosphorescence lifetime. Since this probe is distributed inside the tubular cells of the mice kidney, we succeeded in detecting acute renal hypoxic conditions and chronic kidney disease. This technique enabled us to estimate intracellular partial pressures of oxygen in vivo by extrapolating the calibration curve generated from cultured tubular cells. Since intracellular oxygen tension is directly related to cellular hypoxic reactions, such as the activation of hypoxia-inducible factors, our method will shed new light on hypoxia research in vivo.

Polymer-ceramic nanocomposites based on new concepts were developed for embedded capacitor applications. The dielectric constant was above 80 at 1 MHz and the specific capacitance was successfully achieved 8 nF/cm 2 . By use of this nanocomposites, multilayer printed wiring boards with embedded passive components were fabricated for prototypes. The following technologies would be reported in this conference. Firstly, based on the investigation of barium titanate (BaTiO 3 ) crystallites, various particles with the sizes from 17 to 100 nm were prepared by the two-step thermal decomposition method from barium titanyl oxalate (BaTiO(C 2 O 4 ) 2 ·4H 2 O). It was clarified that BaTiO 3 particles with a size of around 70 nm exhibited a maximum dielectric constant of over 15,000. Secondary, the BaTiO 3 surface modification based on a new concept was applied to improve the affinity between BaTiO 3 particles and polymer matrix. Thirdly, the blend polymer of an aromatic polyamide (PA) and an aromatic bismaleimide (BMI) was employed as the matrix from a view-point of both the processability during fabricating the substrates with embedded passive components and the thermal stability during assembling LSI chips. Finally, these technologies were combined and optimized for embedded capacitor materials.

A novel fabrication of hierarchically ordered organic and inorganic hybrid structures at length scales ranging from nanometers to micrometers was demonstrated by oxygen plasma treatment of self-organized silicon-containing block copolymer films. The rod-coil type silicon-containing block copolymer, polystyrene-b-polyisoprene with polyhedral oligomeric silsesquioxane (POSS) -modified side chains, was successfully synthesized by hydrosilation of polystyrene-b-poly(1,2-ran-3,4-isoprene) block copolymer with hydrido-heptacyclopentyl substituted POSS. The films were prepared from the polymer solution by casting on silicon wafers under a moist air flow. The self-organized microstructures were investigated by electron microscopy. It was found that the hexagonally packed micropores and phase-separated nanodomains were formed within the films. Oxygen plasma etching of the films provided novel hierarchically ordered hybrid structures.

A rapid growth of mixed-signal integrated circuits is driving the needs of multifunction and miniaturization of the component in electronics applications. Polymer-ceramic composites have been of great interest as embedded capacitor materials because they enabled companies to combine the processability of polymers with the high dielectric constant of ceramics. This paper presents the preparations and performance characterizations of novel polymer-ceramic nanocomposites based on new concepts for embedded capacitor application. First, metal particle nickel-filled nanocomposite with high dielectric constant was evaluated as a candidate for embedded capacitors. Two types of nickel particles were selected with the size of 400 and 150nm, respectively. With proper filler loading and highly dispersed, a high dielectric constant of over 90 was observed with a filler loading ratio of 60-vol%. Second, the surface modification of a barium titanate (BTO) particle was also attempted in nanocomposite. Phthalocyanine-coated BTO (Pc-coated BTO) was selected as filler to prepare the composite. Its dielectric constant was observed as over 80 at 1MHz, which was much higher than that of composite derived from commercial BTO. Last, in order to improve the processability of the nanocomposite, 4, 4'-diphenylmethane bismaleimide (BMI) was selected as a matrix polymer by the combination with polyamide (PA). Higher dielectric constant nanocomposite derived from PA/BMI and Pc-coat BTO was obtained, and its potential application towards embedded capacitors was also evaluated.

Two new nitrile-containing diamine monomers, 4-[bis(4-aminophenyl)amino]benzonitrile and 4-[4-(1-cyanopropoxy)phenyl]2,6-bis(4-aminophenyl)pyridine were synthesized. The diamine monomers were reacted with various tetracarboxylic dianhydrides, followed by cyclodehydration (imidization) without isolation to produce a series of novel polyimides with pendant nitrile groups on the side chain. The polymers were obtained in quantitative yields with high molecular weight. Among them, polymers derived from ODPA and 6FDA showed good solubility, they could dissolve in polar solvents such as DMF, NMP, DMSO and even pyridine and m-cresol. These tough, transparent and flexible polyimide films had a tensile strength of 80–120 MPa, an elongation at break of 4–12% and a tensile modulus of 1.2–2.3 GPa. The polymers obtained exhibited high glass transition temperatures between 305 and 360 C. Moreover, they were fairly stable up to a temperature around or above 400 C and lost 10% weight in the range of 500–590 C and 470–580 C in nitrogen and air, respectively. Together the dielectric constants of the polyimides were measured to be 3.10–3.73 at 10 GHz. On the other hand, blank polyimides with no – CN groups were also prepared for comparison and the results revealed that the nitrile group affected the thermal property of polyimides as well as the electrical properties. Introduction of the –CN groups would increase the glass transition temperature and also the dielectric constant.

We describe the synthesis, characterization, and lithographic performance of positive-working chemically amplified photosensitive polybenzoxazoles (PSPBOs) composed of partially tert-butoxycarbonyl (t-BOC) protected hyperbranched poly(o-hydroxyamide)s (HB-tbocPHAs) and diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate (DIAS) as a photo-acid generator (PAG). The HB-tbocPHAs as precursors of PSPBOs were synthesized from hyperbranched poly(o-hydroxyamide)s (HBPHAs), which were prepared by self-polycondensation of an AB 2 type monomer. A series of HB-tbocPHAs having the t-BOC content of 8-100 mol % were successfully prepared by controlling the feed amount of di-tert-butyl dicarbonate (DTBDC). HB-tbocPHAs had adequate dissolution rate in tetramethylammonium hydroxide (TMAH) aqueous solution as well as excellent solubility in common organic solvents. HB-tbocPHA having 39 mol % t-BOC group showed the optimum dissolution rate in 2.38 wt% TMAH aqueous solution and good adhesion on a silicon wafer. The thermal deprotection of the t-BOC group and conversion to polybenzoxazole (PBO) of HB-tbocPHA in the presence of strong acid such as p-toluenesulfonic acid (p-TsOH) were investigated by using FT-IR, DSC, and TGA to examine the acid effect. Both the deprotection of t-BOC groups and the conversion to PBO were accelerated in the presence of p-TsOH. The photolithographic performance of the resist formulated with HB-tbocPHA and 20 wt % of DIAS was evaluated. The resist showed 115 mJ/cm 2 of sensitivity and 2.2 of contrast with 365 nm light when it was developed in 2.38 wt % TMAH aqueous solution at room temperature. The fine positive pattern was obtained at the 200 mJ/cm 2 of i-line exposure. The patterned film was successfully converted to polybenzoxazole without any distortion by thermal treatment at 300 °C for 1 h.

Hyperbranched polysiloxysilane (HBPS) terminated by the vinyl functional group was synthesized by the self polymerization of AB2 monomer, 1,5-divinyl-1,1,3,5,5-pentamethyltrisiloxane, in the presence of the platinum catalyst. The terminal vinyl group was converted to 2-hydroxyethyl by the reaction with 9-BBN as the hydroboration reagent. The terminal function was then modified to the 2-bromoisobutyryl group by the reaction of hydroxyl group with 2-bromoisobutyryl bromide. The obtained HBPS possessing the 2-bromoisobutyryl terminal group was immobilized on the silica surface by mixing the silica bead and HBPS in hexane. Block copolymer of HBPS and poly(N-isopropylacrylamide) (PIPAAm) was synthesized by the atom transfer radical polymerization (ATRP) using 2-bromoisobutyryl terminated HBPS as a macroinitiator. The molecular weight of the block copolymer was Mn=23,500 and Mw/Mn=1.31. Graft polymerization of N-isopropylacrylamide on the silica surface was carried out on the 2-bromoisobutyryl terminated HBPS immobilized silica bead using ATRP. The PIPAAm grafted silica bead was applied to the column packed material for temperature-responsive HPLC. Two kinds of steroids, hydrophilic and hydrophobic, were successfully separated by the HPLC system.