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Background: Several kinds of tapes are used for postoperative wounds, which occasionally cause contact dermatitis and result in noticeable pigmentation. A comparison of the postoperative course between different tapes has not been reported. This study aimed at investigating the differences between two postoperative tapes used after breast reconstruction with silicone materials for simple mastectomy. Materials and Methods: Eighty-eight nonconsecutive patients undergoing tissue expander operation and 75 nonconsecutive patients undergoing tissue expander and silicone breast implant operations were included in this prospective study. Two postoperative tapes were used: a nonwoven surgical tape (Yu-ki ban®) or a hypoallergenic polyester-woven fabric tape (Atofine TM), which have different base materials, a removed keratinocyte area, and moisture permeability. We determined the differences in the incidence of skin complications, scar width, and aesthetic results with respect to scarring between the patients using Yu-ki ban and those using Atofine. Results: Statistically similar results were achieved for the patients who underwent reconstruction using either the tissue expander or silicone breast implant. Scar width was similar between the groups; however, the incidence of skin complications was significantly lower in patients using Atofine than in those using Yu-ki ban. Aesthetic results with respect to scarring were better in patients using Atofine than in those using Yu-ki ban, with a significant difference in the incidence of pigmentation between the groups. Conclusion: The tape with higher moisture permeability and a lower removed keratinocyte area should be used to reduce the incidence of contact dermatitis and achieve better aesthetic results with respect to scarring.

Breast reconstruction using a pedicled transverse rectus abdominis muscle (TRAM) flap is a well-established surgical procedure. Although studies suggest that transplanting this flap using a delayed method reduces the risk of partial flap necrosis, challenges persist. Hence, we present three cases of breast reconstruction using a pedicled TRAM flap with both delaying and supercharging. Patient age, excised tissue volume for mastectomy, and follow-up period were as follows: Case 1, 58 years, 429 cm(3), 5 months; Case 2, 35 years, 910 cm(3), 6 months; and Case 3, 56 years, 489 cm(3), 4 months. One patient (Case 2) required a large flap tissue volume to achieve breast symmetry, whereas the other two (Cases 1 and 3) had long, longitudinal scars from previous cesareans sections. In a delayed surgery, the flap was partially elevated with partial dissection and no ligation of the deep inferior epigastric artery and vein (DIEAV). An artificial dermis with a silicone membrane (Teldermis(®)) was used to prevent adhesion of the rectus abdominal muscles and DIEAV to the surrounding tissue. Supercharging was performed by anastomosis between the ipsilateral DIEAV and internal thoracic AV. Flaps in zones I–III and in half of zone IV for Case 2, and zones I–III for Cases 1 and 3, were transferred; all survived without infection. This method allowed the transferring of a larger tissue volume compared with the conventional pedicled TRAM flap-transfer method. Thus, it may be useful for patients who require larger tissue volume or high-risk patients.

BACKGROUND: In silicone breast implant (SBI)-based breast reconstructions, aesthetic outcomes are often low due to the visible upper edge of the SBI. To ameliorate this, grafting fat harvested from the SBI operative field has not been reported to date. Therefore, we aimed to develop a novel technique for fat onlay-grafting, harvested from the inframammary fold (IMF) of the reconstructed breast, and investigate its usefulness. METHODS: A total of 90 patients who underwent SBI-based breast reconstruction after a simple mastectomy were included in this study. The harvested fat was recorded by weight and grafted evenly to the medial and median upper edge of the SBI on the pectoralis major muscle. We applied this technique to 30 patients (fat onlay-grafting group) and compared them with the 60 patients (no-grafting group) who did not undergo our technique using the postoperative 1-year aesthetic outcome scores of the medial and median upper edge of the SBI. Furthermore, we investigated the correlation between the weight of harvested fat and body mass index. RESULTS: No postoperative wound complications occurred, and infection, hardened fat, and fat lysis were not found in the fat onlay-grafting group. The medial and total aesthetic outcome scores in the fat onlay-grafting group were significantly higher than those in the no-grafting group (P

Background: Various flap monitoring techniques have been used in the early detection of anastomotic thrombus; however, the use of automatic and continuous monitoring methods is presently uncommon. The purpose of this study was to investigate trends in interstitial fluid glucose concentration (IFG) in flap monitoring by measuring IFG automatically and continuously. Methods: Nine patients underwent unilateral breast reconstruction using a transverse rectus abdominis myocutaneous flap with vascular anastomosis. Two IFG measuring devices were attached to each patient. One device was attached to the flap (flap IFG) and the other to the healthy breast (control IFG). In each case, flap IFG, control IFG, and IFG ratio (flap IFG/control IFG) were recorded in the initial 72 h post-surgery (first half) and also in the subsequent 72 h (second half). In all of the cases, the mean values recorded in the first half and those in the second half were compared. Results: All flaps survived. The flap IFG didn’t fall below 40 mg/dL in the first half. The minimum flap IFG and IFG ratio were 42 mg/dL and 0.55 in the first half. The flap IFG was significantly higher in the first half than in the second half in all cases, and the IFG ratio was similar in 8 cases. Furthermore, mean flap IFG and mean IFG ratio in all cases in the first half were significantly higher than in the second half. Conclusions: IFG measurements may complement conventional flap monitoring, particularly in the early postoperative period.

Split-thickness skin grafts constitute an established and widely used procedure for treating skin ulcers. However, in patients on anticoagulation therapy, wound healing abnormalities can prevent smooth epithelialization of their donor site. We aimed to investigate the usefulness of a technique to facilitate smooth wound healing through partial dimension reduction, and spared skin grafts back of donor sites with split-thickness skin grafts for patients undergoing anticoagulation therapy and investigate its usefulness. Partial dimension reduction and spared skin grafting back was performed on the donor site in 4 cases (group A), and the conventional method (moist dressing) was performed in 3 cases (group B). We compared the time to achieve complete epithelialization, the degree of pain, the frequency of dressing changes during the perioperative period, and the cosmetic results 6 months after surgery in both groups. The spared skin graft achieved good circulation. The time to achieve complete epithelialization was 3.1 weeks (2.5-4 weeks) in group A and 5.7 weeks (3-8 weeks) in group B; group A tended to experience less pain and fewer dressing changes during the perioperative period than group B. In addition, group A yielded superior cosmetic results to group B. Our technique can contribute to increasing the defense against physical stimulation in the donor site. Therefore, rapid wound healing and easy wound management can be achieved. We believe that it may be useful in split-thickness skin grafts for patients undergoing anticoagulation therapy.

Pendant carboxyl groups were introduced into donor–acceptor polyfluorene carrying benzothiadiazole as an acceptor moiety. The emission color from its solution was different depending on the solvent. While the methanol solution of the polymer exhibited blue emission, yellow emission was observed from its tetrahydrofuran solution. Influence of solvent polarity, solution concentration, temperature, and addition of acid on photoluminescence properties indicated that the observed change in emission color was due to polymer aggregation coming from inter and/or intramolecular interaction between pendant carboxyl groups. Polyfluorene carrying benzothiadiazole moiety with pendant amino groups also exhibited emission color change and was useful as a fluorimetric sensor for polyacid.

Cross-linked solid polymer electrolytes (cross-linked SPEs) composed of poly(ethylene glycol) dimethyl ethers (PEGDMEs) with various molecular weights and high molecular weight poly(ethylene oxide) (PEO), Acryl-HBP having various ethylene oxide (EO) units (3EO (n = 3), 4EO (n = 4), 6EO (n = 6), 11EO (n = 11)), and LiN(SO2CF3)2 salt were prepared by using radical initiator and electron beam (EB) irradiation. The effects of molecular weights of PEGDMEs and PEO, EO units in the Acryl-HBP, crosslinking methods, and EB irradiation intensity on the ionic conductivity and mechanical property for the cross-linked SPEs were investigated. Ionic conductivities of the cross-linked SPEs composed of Acryl-HBP having 4EO (n = 4) units and PEGDME with molecular weight of 500 were found to be 1.24 × 10−4 S/cm at 20 °C and 1.97 × 10−3 S/cm at 80 °C for benzoyl peroxide radical initiator and to be 2.44 × 10−4 S/cm at 20 °C and 3.22 × 10−3 S/cm at 80 °C for EB irradiation, respectively. Further addition of a copolymer (EO-AGE) of ethylene oxide with allyl glycidyl ether improved mechanical properties of the cross-linked SPE, and provided mechanical strength suitable for practical lithium battery application. The Li4Ti5O12/cross-linked SPE/LiFePO4–C cell was assembled by using the cross-linked SPE modified with EO-AGE, and the battery performance was evaluated. The battery showed reversible charge-discharge capacity of 42 mAh at 25 °C and C/10 rate.

Poly(2,2-dimethoxypropylene carbonate) (poly-1) was synthesized by bulk polymerization of 2,2-dimethoxypropylene carbonate (1) with bis(octanoic acid) Tin (II) salt (Sn(Oct)2). The polymer electrolytes composed of poly-1 with lithium salts such as lithium bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2, LiTFSI) and lithium bis(fluorosulfonyl)imide (LiN(SO2F)2, LiFSI) were prepared, and their ionic conductivities, thermal and electrochemical properties were investigated. Polymer electrolytes at the [Li salt]/[repeating unit (RU)] ratio of 1/1 showed the ionic conductivity of 3.53 × 10− 4 S/cm at 80 °C and 1.08 × 10− 4 S/cm at 30 °C for the poly-1/LiFSI system and of 1.23 × 10− 5 S/cm at 80 °C and 1.62 × 10− 7 S/cm at 30 °C for the poly-1/LiTFSI system, respectively. Ionic conductivities of both polymer electrolytes increased with an increase in the lithium salt concentrations, but their glass transition temperatures (Tg) decreased. Transference numbers of lithium ion (t+) of the polymer electrolytes are 0.56 for the poly-1/LiTFSI system and 0.75 for the poly-1/LiFSI system, respectively. The polymer electrolytes for the poly-1/LiTFSI system were thermally more stable than those for the poly-1/LiFSI system. Decomposition temperatures of the polymer electrolytes decreased with lithium salt contents. Both polymer electrolytes had electrochemical stabilities up to 4 V. The Li/polymer electrolyte/LiFePO4 cell by using polymer electrolyte film at the [Li salt]/[RU] ratio of 1/1 for the poly-1/LiFSI system showed the capacity of 100 mAh/g at 60 °C and 0.01C.

Wound edge–based propeller perforator flaps have often been applied to soft tissue reconstruction of sacral pressure sores. Although this flap often causes necrosis due to overtension and twisting of the perforators, salvage surgery using a postoperative delay technique has not been reported thus far. In this article, we present a case in which we successfully reconstructed a sacral pressure sore using a wound edge–based propeller perforator flap. The flap caused severe congestion, which had a concern due to the potential wide-ranging flap loss; it was subsequently salvaged by an emergent delay procedure and negative-pressure wound therapy on day 2 postoperatively.

Poly(butylene sulfite) (poly-1) was synthesized by cationic ring-opening polymerization of butylene sulfite (1), which was prepared by the reaction of 1,4-butanediol and thionyl chloride, with trifluoromethanesulfonic acid (TfOH) in bulk. The polymer electrolytes composed of poly-1 with lithium salts such as bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2, LiTFSI) and bis(fluorosulfonyl)imide (LiN(SO2F)2, LiFSI) were prepared, and their ionic conductivities, thermal, and electrochemical properties were investigated. Ionic conductivities of the polymer electrolytes for the poly-1/LiTFSI system increased with lithium salt concentrations, reached maximum values at the [LiTFSI]/[repeating unit] ratio of 1/10, and then decreased in further more salt concentrations. The highest ionic conductivity values at the [LiTFSI]/[repeating unit] ratio of 1/10 were 2.36 × 10−4 S/cm at 80 °C and 1.01 × 10−5 S/cm at 20 °C. On the other hand, ionic conductivities of the polymer electrolytes for the poly-1/LiFSI system increased with an increase in lithium salt concentrations, and ionic conductivity values at the [LiFSI]/[repeating unit] ratio of 1/1 were 1.25 × 10−3 S/cm at 80 °C and 5.93 × 10−5 S/cm at 20 °C. Glass transition temperature (T g) increased with lithium salt concentrations for the poly-1/LiTFSI system, but T g for the poly-1/LiFSI system was almost constant regardless of lithium salt concentrations. Both polymer electrolytes showed high transference number of lithium ion: 0.57 for the poly-1/LiTFSI system and 0.56 for the poly-1/LiFSI system, respectively. The polymer electrolytes for the poly-1/LiTFSI system were thermally more stable than those for the poly-1/LiFSI system.

Unsymmetrical 7-(2′-bromoethoxycarbonyl)-7,8,8-tris(methoxycarbonyl)-p-quinodimethane (2) underwent a quantitative intermolecular [6 + 6] photocycloaddition reaction through a single crystal-to-single crystal transformation to afford a bridge-substituted [2.2]paracyclophane (3). The crystal structure of 2 indicates that the bromoethoxy groups conveniently form σ-halogen bonds with the carboxyl groups to yield 2-fold helical assemblies of an isolated pair of 2. 3 has a relatively long distance between bridged carbon–carbon bonds in comparison with the known ones. Such bonds caused an one-side insertion reaction of molecular oxygen in solution to afford the peroxide bridge-substituted [2.2]paracyclophane in a quantitative yield.

Polymer electrolytes based on vinyl ethers with various ethyleneoxy (EO) chain length (poly-1a (m = 3), poly-1b (m = 6), poly-1c (m = 10), and poly-1d (m = 23.5)) with lithium bis(trifluoromethanesulfonimide) (LiTFSI) were prepared, and effect of pendant EO chain length in the polymers on electrochemical and thermal properties was investigated. Glass transition temperature (T g) of all polymer electrolytes increased linearly with an increase in salt concentrations. Ionic conductivities of the polymer electrolytes increased with an increase in the pendant EO chain length of the polymers at the constant [Li]/[O] ratio, but in the polymer electrolyte of the poly-1d (m = 23.5) with the longest pendant EO chain length, ionic conductivity decreased in the low temperature range of −20 to 10 °C due to the crystallization of the pendant EO chain. The highest ionic conductivity, 1.23 × 10−4 S/cm at 30 °C, was obtained in the polymer electrolyte of the poly-1c (m = 10) with pendant EO chain length of 10 at the [Li]/[O] ratio of 1/20. It was found that the cross-linking of the polymer electrolyte, composed of poly-1c (m = 10) with LiTFSI at the [Li]/[O] ratio of 1/28, by electron beam (EB) irradiation may improve the mechanical property without affecting ionic conductivity, thermal property, and oxidation stability. Polymer electrolytes based on poly-1a (m = 3), poly-1b (m = 6), poly-1c (m = 10), and poly-1d (m = 23.5) and cross-linked polymer electrolytes were electrochemically stable until 4 V and thermally stable around 300 °C.

The composites of polystyrene sulphonic acid (PSS) with various organic dyes were coated on a polyethylene terephthalate (PET) film. The coated film exhibited colour change depending on humidity. The composite of PSS with Neutral Red showed colour change from blue (low humidity) to pink (high humidity) in a similar way to that of conventional cobalt-based humidity indicator. The change of colour was evaluated using L*a*b* coordinates and the results revealed that the composite of PSS with brilliant blue FCF gave the most distinct colour change. Further, addition of hygroscopic inorganic salt such as magnesium chloride was found to be effective in tuning humidity range.

7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes with bulky aryloxy groups such as benzyloxy (1a), pentafluorobenzyloxy (1b), and both benzyloxy and pentafluorobenzyloxy (1c) were synthesized. We investigated effects of these bulky groups on thermal solid-state polymerization reactivities on the basis of crystal structures of 1a–1c. Thermal polymerizations gave 1,6-trans-type stereoregular polymers in quantitative yields in 1 day at 110 °C for 1a, 1 day at 150 °C for 1b, and 6 days at 110 °C for 1c. Their initial crystal shapes were retained in appearance during polymerization to yield solid bundle assemblies of their polymeric chains. X-ray single-crystal structure analysis indicates that their crystals adopt molecular arrangements suitable for one-dimensional polymerization with the 1,6-trans-type addition along one crystallographic axis. Such arrangements led to expansion polymerization of 1b and contraction one of 1c. The resulting stereoregular polymers form less ordered bundle assemblies than tho...

7-Cyano-7-(2′-haloethoxycarbonyl)-1,4-benzoquinone methides bearing 2′-haloethoxy groups such as 2′-fluoroethoxy (1a), 2′-chloroethoxy (1b), 2′-bromoethoxy (1c), and 2′-iodoethoxy (1d) were synthesized. The halogen atoms of the haloalkoxy group in the quinone methide skeleton greatly affected their crystal structures, which belong to space group P21/c for 1a, P21/a for 1b, and P-1 for 1c and 1d. The thermal solid-state polymerizations in vacuo at 60 or 80 °C gave amorphous polymers with regular head-to-tail configuration and proceeded with retention of the crystal shapes in appearance. Relations between the molecular assembly modes and the polymerization modes indicate that 21 (2-fold) assemblies of 1b are able to undergo 21 helical polymerization with handedness.

Dopamine transporter single photon emission CT (DAT-SPECT) is useful in the evaluation of dementia with Lewy bodies (DLB). The specific binding ratio (SBR) is an index to measure DAT density. However, poorly reproducible cases are occasionally experienced in clinical practice. We hypothesized that distance-weighted histogram (DWH) may be useful to improve the reproducibility of SBR. The purpose of this study was to investigate inter- and intra-observer reproducibility of SBR with conventional and DWH methods, and to visually evaluate the precision in reference voxel of interest (VOI) definition using these methods. This study included 50 adult patients with probable DLB. They underwent brain MRI, DAT-SPECT, and cerebral blood flow SPECT with N-isopropyl-p-[123I]iodoamphetamine (I-123 IMP). SBR of the striatum was calculated using conventional and DWH method. For inter-observer reproducibility validation, conventional and DWH SBR were independently evaluated by experienced nuclear medicine physicians; these measurements were repeated by the nuclear medicine physician to investigate intra-observer reproducibility. Proper reference VOI definition was achieved in 60.0% using conventional SBR and in 98.0% with DWH SBR. Both conventional and DWH SBR demonstrated good inter- and intra-observer reproducibility, however, there were statistically significant inter- and intra-observer variations with conventional SBR measurements. Average inter- and intra-observer errors of conventional SBR were 7.9 and 6.1%, respectively. Conversely, DWH SBR errors were not observed in all patients. Moreover, average inter- and intra-observer errors were significantly higher in conventional SBR with improper reference VOI definition than in that with proper reference VOI definition. Although the reproducibility of conventional and DWH SBR was good, inter- and intra-observer bias could not be ignored in conventional SBR, particularly with improper reference VOI definition. Thus, DWH may be useful to improve inter- and intra-observer reproducibility of SBR.

Symmetrical 7,7,8,8-tetrakis(alkoxycarbonyl)-p-quinodimethanes with methoxy(1a(Me)) and ethoxy(1b(Et)) as alkoxy groups formed 1:1 charge-transfer complex crystals with an asymmetrical quinoid compound, N,7,7-tricyanoquinone methide imine (2). The 1:1 formation of the crystals was ascertained on the basis of 1H NMR spectroscopy and single crystal X-ray structure analysis. These 1:1 charge-transfer complex crystals (1a(Me)/2 and 1b(Et)/2 monomer cocrystals) underwent photochemical and thermal polymerizations via a radical mechanism with keeping initial crystal shapes in appearance to form stereoregular alternating copolymers in quantitative yields. The stereoregular alternating copolymers formed bundle assemblies in the less order state. The formation of stereoregular alternating copolymers was explained on the basis of the structures of the monomer cocrystals solved by X-ray crystallography. Less-ordered bundle assemblies are considered to be formed by findings that the gravity of each component is not aligned on a straight line within the one-dimensional column with alternating stacked arrangements of 1a(Me) or 1b(Et) and 2 in the crystals, which are caused by asymmetrical 2.

Polyfluorenes with pendant allyl groups were prepared by terpolymerization of 9,9-dihexylfluorene-2,7-bis(trimethyleneborate), 2,7-dibromo-9,9-bis(2-allyloxyethyl)fluorene, and 4,7-dibromo-2,1,3-benzothiazole, or 4,7-dibromo-2,1,3-naphthoselenadiazole using Suzuki coupling reaction. The subsequent hydrosilylation reaction of these precursor polymers with ethoxydimethylsilane quantitatively converted the allyl groups to ethoxysilyl groups. Hybridization of the emitting polyfluorenes with silicone was successfully achieved by the solvent-free sol–gel reaction of tetraethoxysilane and silanol-terminated polydimethylsiloxane in the presence of the ethoxysilyl-functionalized polyfluorenes. Fluorescence spectra of these luminescent silicones revealed that emitting polyfluorenes were dispersed homogeneously in the matrix of silicone without aggregation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 622–628

Substituted 7-aryl-2,6-dimethyl-1,4-benzoquinone methides which have an electron-donating methoxy substituent at the para-position (p-OMe, 2a) or an electron-withdrawing chloro one at the para- (p-Cl, 2b), meta- (m-Cl, 2c), and ortho-positions (o-Cl, 2d) of the benzene ring were synthesized, and their asymmetric anionic polymerizations using the complex of lithium 4-isopropylphenoxide with (−)-sparteine were carried out in toluene at 0 °C. The polymers with negative specific rotation were obtained for all of four monomers, and the polymer obtained from 2a showed smaller specific rotation value than that of polymer having no substituent (p-H, 1) on the phenyl group and the polymers obtained from 2b–d showed larger ones. It was found that the kind of a substituent and its substitution position on the phenyl group affect significantly the optical activity of polymers. The largest specific rotation value of [α]435= −153.2° was obtained in the polymerization of 2d with an ortho-chloro substituent. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 437–444

Polymer electrolytes composed of poly(ethylene oxide) and a polyanionic lithium salt are prepared, and electrochemical and thermal properties were investigated in the absence and presence of BF 3 ·OEt 2 . The addition of BF 3 ·OEt 2 increases the ionic conductivities, and the lithium ion transference number of the polymer electrolyte for the PEO/poly(lithium acrylate) (PLA) and PEO/poly(lithium vinylsulfonate) (PLVS) system were higher than that of PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) system. However, ionic conductivities of the polymer electrolyte in the presence of BF 3 ·OEt 2 for the PEO/PLVS system were higher than that for the PEO/PLA system below 50 °C, due to the suppression of the crystallization of PEO. It was found that the structure of functional group in polyanionic lithium salts significantly affect electrochemical and thermal properties of polymer electrolytes.

Alternating copolymers (poly(1a- g - alt -VC)) of vinyl ethers with various methoxy oligo(ethyleneoxy)ethyl groups and vinylene carbonate (VC) were prepared, and the thermal and electrochemical properties of their polymer electrolytes with LiTFSI and interfacial stability between the polymer electrolyte and Li metal electrode were investigated. T g 's increased linearly with salt contents, and decreased with an increase in the chain length of methoxy oligo(ethyleneoxy)ethyl groups in the vinyl ethers at constant salt concentration. The slopes of T g vs. [Li]/[O] were identical, independent of the polymer structure. The ionic conductivities of the polymer electrolytes increased with increasing the side-chain ethyleneoxy (EO) unit length of the vinyl ether unit in the alternating copolymers, and also their temperature dependences became relatively smaller in the polymer electrolytes having longer EO units in the vinyl ethers. The highest ionic conductivity, 1.2 × 10 −4 S/cm at 30 °C, was obtained in the alternating copolymer with a side-chain EO unit length of 23.5 in the vinyl ether unit. Ion transport coupled with the segmental motion of the polymer is dominant in these polymer electrolytes. Interfacial resistance increased gradually with contact time, indicative of the formation of passivation films on the Li metal electrode. These polymer electrolytes are thermally stable and have large electrochemical windows of use.

Polycarbonates (4a–d) with various side chain lengths were synthesized by the reaction of 1,4-bis(hydroxyethoxy)benzene derivatives and triphosgene in the presence of pyridine. The polymer electrolytes composed of 4a–d with lithium bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2, LiTFSI) were prepared, and their ionic conductivities and thermal and electrochemical properties were investigated. 4d-Based polymer electrolyte showed the highest ionic conductivity values of 1.0 × 10−4 S/cm at 80 °C and 1.5 × 10−6 S/cm at 30 °C, respectively, at the [LiTFSI]/[repeating unit] ratio of 1/2. Ionic conductivities of these polycarbonate-based polymer electrolytes showed the tendency of increase with increasing the chain length of oxyethylene moieties as side chains, suggestive of increased steric hindrance by side chains. Unique properties were observed for the 4a(n = 0)-based polymer electrolyte without an oxyethylene moiety. All of polycarbonate-based polymer electrolytes showed good electrochemical and thermal stabilities as polymer electrolytes for battery application.

A novel water-soluble cyclic macromonomer, AAm-c-PEG, based on a cyclic poly(ethylene glycol) (PEG) was prepared. Radical copolymerizations of N-isopropylacrylamide (NIPAAm) with the cyclic macromonomer were carried out to obtain mechanically cross-linked poly(NIPAAm) hydrogels with movable cross-linking points. For comparison, chemically cross-linked PEG-grafted poly(NIPAAm) hydrogels were prepared by radical copolymerization of NIPAAm with a PEG-based linear macromonomer, AAm-l-PEG, using methylenebis(acrylamide) (MBAAm) as a cross-linking agent. Shrinking experiment of these hydrogels revealed poly(NIPAAm) gels with movable cross-linking points exhibited faster volume shrinking than those of chemically cross-linked ones. Further, threading efficiency for cyclic PEG segment was estimated by measuring the swelling ratio in isopropyl alcohol (IPA) which is a nonsolvent for PEG.

Asymmetric anionic polymerizations of 7-cyano-7-alkoxycarbonyl-1,4-benzoquinone methides (1) with various alkoxy groups were performed using chiral initiators such as lithium isopropylphenoxide (iPrPhOLi)/(S)-(–)-2,2′-isopropylidene-bis(4-phenyl-2-oxazoline) ((–)-PhBox) and lithium isopropylphenoxide (iPrPhOLi)/(–)-sparteine ((–)-Sp) to investigate the effect of the alkoxy groups of alkoxycarbonyl substituent in the monomers 1 and chiral ligands of chiral initiators on the control of chiral center in the formation of polymers. Molar optical rotation values of the polymers were significantly dependent upon alkoxy groups, and the polymers with higher molar optical rotation were obtained in monomers with primary alkoxy groups. The asymmetric anionic oligomerizations of the quinone methides having methoxy(1a), ethoxy(1b), and n-propoxy(1c) groups with chiral initiators were carried out. Both 1-mers and 2-mers were isolated and their optical resolutions were performed to determine the extent of stereocontrol. High stereoselectivity was observed at the propagation reaction, but not at the initiation reaction. The effect of the counterion on the control of chiral center in the formation of the polymer was investigated in the asymmetric anionic polymerizations of 1b with iPrPhOM(M = Li, Na, K)/(–)-Sp and iPrPhOM(M = Li, Na, K)/(–)-PhBox initiators and discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Asymmetric anionic polymerizations of a prochiral monomer, 7-cyano-7-phenyl-1,4-benzoquinone methide (3), using chiral initiators were performed under various conditions, and optically active polymers having configurational chirality in the main chain were obtained though their specific rotation values are quite small. The optically active polymer with a negative specific rotation value of −4.4° was obtained by polymerization of 3 with a lithium isopropylphenoxide (iPrPhOLi)/(−)-sparteine ((−)-Sp) in a mixture solution of dichloromethane/toluene ratio of 30/70 (in vol%) at −40 °C. Stereostructures of 1-mer, 2-mer, and oligomers obtained by asymmetric anionic oligomerization of 3 with iPrPhOLi/(−)-Sp were examined in detail. It was found that the stereoselectivity turned out to be the opposite between the initiation reaction and the propagation one.

OBJECTIVE Continuous hemodiafiltration is frequently used in intensive care as renal replacement therapy for acute kidney damage. Recent studies have shown that increased flow rates can effectively increase survival. However, continuous hemodiafiltration also removes essential small molecules such as amino acids. METHODS We compared amino acid loss between conventional (normal-flow) and high-flow continuous hemodia-filtration in 17 patients admitted to the intensive care unit for conditions such as sepsis. Patients were randomly divided into a normal-flow group (dialysate flow, 500 mL/min; filtrate flow, 300 mL/min; and blood flow, 80 mL/min) and a high-flow group (dialysate flow, 1,500 mL/min; filtrate flow, 900 mL/min; blood flow, 100 mL/min). Blood samples were collected immediately prior to continuous hemodiafi initiation, and at 2 and 6 hours after con-tinuous hemodiafiltration initiation. In addition, blood and filtrate were collected from the circuit in front of and behind the continuous hemodiafiltration dialyzer. RESULTS We found that amino acid removal was significantly higher in the high-flow group and that amino acids were removed into the filtrates in proportion to their plasma concentrations. Furthermore, plasma amino acid con-centrations also tended to decrease with the length of time continuous hemodiafiltration was performed. Given that large amounts of amino acid are removed during continuous hemodiafiltration, plasma amino acid levels should be monitored when prolonged continuous hemodiafiltration is performed. CONCLUSIONS Amino acid loss is particularly high during high-flow continuous hemodiafiltration, suggesting that it may be necessary to shorten the duration of high-flow continuous hemodiafiltration or supplement patients with sufficient amounts of amino acids.

アクリル酸 t-ブチルのリビングアニオン重合を利用して，α 位にヒドロキシル基，ω 位にカルボキシル基を有するスチリル基含有ポリアクリル酸 t-ブチルを合成した．次に，その分子内環化反応を高度希釈条件下で行い，スチリル基を有する環状ポリアクリル酸 t-ブチルを調製した．最後に，ギ酸で処理することにより，ポリアクリル酸 t-ブチル部位をポリアクリル酸に誘導し，環状ポリアクリル酸に基づいた環状マクロモノマー(St-c-PAA)を得た．St-c-PAA の存在下で，N-イソプロピルアクリルアミド(NIPAAm)のラジカル共重合を行い，共重合過程で起こる糸通しによって形成される可動性架橋ゲルを得た．得られたゲルの膨潤度は水溶液の pH に大きく依存した．このような pH 依存性は，架橋点を構成する環状ポリアクリル酸鎖の構造変化によって，架橋点の可動性が大きく変わったことに起因すると考えられる．

We investigate the flow between co-rotating disks with a narrow gap, enclosed by a stationary shroud at their circumferences, using flow visualisations with PIV analyses. Experiments are conducted at three values of non-dimensional hub radius κ in wide ranges of other two system parameters, namely, disk-tip Reynolds number Re and gap aspect ratio δ. As a result, we reveal stability diagrams concerning core-shape modes of the flow defined by the modal number m. Except for the m = ∞, m decreases with increasing κ, as well as increasing Re and increasing δ. Especially at δ > 0.2, the influence of κ upon m is remarkable. Besides, we find out a new core-shape mode with m of unity, at large Re, large δ and large κ. This core-shape mode 1 is the mode where there exists only one bulk of the fluid in rigidly-rotational motion, which is attached to the hub and travels in the azimuthal direction with a rotation speed less than the disks'.

Novel polyfluorene copolymers with pendant hydroxyl groups, poly[2,7-(9,9-dihexylfluorenel-2,7-(9,9-bis(6-hydroxyhexyl)-fluorene)-co-2,7-(9,9-dihexylfluorene)-1,4-phenylene] (PFP-OH) and poly[2,7-(9,9-dihexylfluorene)-2,7-(9,9-bis/6-hydroxyhexyl)fluorene)-co-2,7-(9,9-dihexylfluorene)-4,7-(2,1,3-benzothiadiazole)] (PFBT-OH) were prepared. Acid-catalyzed polycondensations of tetraethoxysilane were carried out in the presence of these polymers to obtain homogeneous hybrids. Photoluminescence spectra of these hybrids suggested the polymers were immobilized in silica matrix retaining their π-conjugated structures. Further, hybrids of coat film were prepared utilizing perhydropolysilazane as a silica precursor. Their optical properties were examined.

Asymmetric anionic polymerization of a prochiral quinone methide monomer, 7-cyano-7-ethoxycarbonyl-1,4-benzoquinone methide (1), was examined using two chiral anionic initiators, lithium 4-isopropylphenoxide (iPrPhOLi)/(−)-sparteine((−)-Sp) and iPrPhOLi/(S)-(−)-2,2′-isopropylidenebis(4-phenyl-2-oxazoline) ((−)-PhBox) initiators, in a mixture solution of dichloromethane/toluene (30/70 in vol %), and optical activities of the resulting polymers and oligomers (1-mer and 2-mer) were investigated in detail. On asymmetric anionic polymerization of 1 with iPrPhOLi/(−)-Sp initiator, stereoselectivity was quite low on both initiation and propagation reactions, while in the case of iPrPhOLi/(−)-PhBox initiator, stereoselectivity was quite low on the initiation reaction, but the propagation reaction proceeded stereoselectively, resulting in an optically active polymer of 1 (poly(1)) with a large positive specific rotation.

The cross-linked composite solid polymer electrolytes composed of poly(ethylene oxide), lithium salt (LiN(SO2CF3)2), and a hyperbranched polymer whose repeating units were connected by ether-linkage (hyperbranched polymer (HBP)-2) were prepared, and their ionic conductivity, thermal properties, electrochemical stability, mechanical property, and chemical stability were investigated in comparison with the non-cross-linked or cross-linked composite solid polymer electrolytes using hyperbranched polymers whose repeating units were connected by ester-linkage (HBP-1a, 1b). The cross-linked composite solid polymer electrolyte using HBP-2 exhibited higher ionic conductivity than the non-cross-linked and cross-linked composite solid polymer electrolytes using HBP-1a and HBP-1b, respectively. The structure of the hyperbranched polymer did not have a significant effect on the thermal properties and electrochemical stability of the composite solid polymer electrolytes. The tensile strength of the cross-linked composite solid polymer electrolyte using HBP-2 was lower than that of the cross-linked composite solid polymer electrolyte using HBP-1b, but higher than that of the non-cross-linked composite solid polymer electrolyte using HBP-1a. The HBP-2 with ether-linkage showed higher chemical stability against alkaline hydrolysis compared with HBP-1a with ester-linkage.

The hyperbranched polymers (HBP-SA-Acs) with both a sulfonic acid group as a functional group and an acryloyl group as a cross-linker at terminals in different ratios of sulfonic acid group/acryloyl group (SO3H/Ac) were successfully synthesized as a new thermally stable proton-conducting electrolyte. The cross-linked hyperbranched polymer electrolyte membranes (CL-HBP-SAs) were prepared by thermal polymerizations of the HBP-SA-Acs using benzoyl peroxide, and their ionic conductivities under dry condition and thermal properties were investigated. The ionic conductivities of the CL-HBP-SAs were found to be in the range of 2.2 × 10−4 to 3.3 × 10−6 S/cm, depending upon the SO3H unit contents, at 150 °C under dry condition, and showed the Vogel–Tamman–Fulcher (VTF) type temperature dependence, indicating that proton transfer is cooperated by local polymer chain motion. All CL-HBP-SAs were thermally stable up to 260 °C, and they had suitable thermal stability as electrolyte membranes for the high-temperature fuel cells under dry condition. Fuel cell measurement using a single membrane electrode assembly cell with a cross-linked electrolyte membrane was successfully performed under non-humidified condition. It was demonstrated that applying the concept of dry polymer system to proton conduction is one possible approach toward high-temperature fuel cells.

Two different molecular weight hyperbranched polymers (HBP(L)-(PA)2 and HBP(H)-(PA)2) with two phosphonic acid groups as a functional group at the periphery and a low molecular weight hyperbranched polymer (HBP(L)-(PA)2-Ac) with both two phosphonic acid groups and an acryloyl group as a cross-linker at the periphery were successfully synthesized as thermally stable proton-conducting electrolytes. A cross-linked electrolyte membrane (CL-HBP(L)-(PA)2) was prepared by thermal polymerization of the HBP(L)-(PA)2-Ac using benzoyl peroxide. Ionic conductivities of the HBP(L)-(PA)2, the HBP(H)-(PA)2, and the CL-HBP(L)-(PA)2 under dry condition and their thermal properties were investigated, and also, the effect of the phosphonic acid group number on them was discussed. Ionic conductivities of the HBP(L)-(PA)2 and the HBP(H)-(PA)2 were found to be 1.5 × 10−5 S cm−1 at 150 °C and 3.6 × 10−6 S cm−1 at 143 °C, respectively, under dry condition, and showed the Vogel–Tamman–Fulcher type temperature dependence. The hyperbranched polymers and the cross-linked electrolyte membrane were thermally stable up to 300 °C, and the cross-linked electrolyte membrane (CL-HBP-(PA)2) had suitable thermal stability as an electrolyte membrane for the high-temperature fuel cells under dry condition. Fuel cell measurement using a single membrane electrode assembly cell with the cross-linked membrane was performed.

A pentamethylcyclotrisiloxane moiety was introduced into cyclic polystyrene (cPSt) and cyclic PDMS (cPDMS) to obtain noncovalent cross-linking agents, D3-cPSt and D3-cPDMS, respectively. Anionic ring-opening polymerization of octamethylcyclotetrasiloxane (D4) in nitrobenzene was carried out in the presence of D3-cPSt to obtain a cloudy white PDMS gel as a precipitation. On the other hand, bulk copolymerization of D3-cPDMS with D4 proceeded in a homogeneous state to give a colorless transparent PDMS gel in high yield. The formation of mechanically linked PDMS with movable cross-linking was indicated by control experiment. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5882–5890, 2009

Solid-state polymerization of 7,7,8,8-tetrakis(methoxyethoxycarbonyl)quinodimethane (1) was investigated in vacuo by irradiation using a high-pressure mercury lamp at 30 °C. The polymerization of 1 in the solid state took place in very slow rate and reached to a complete conversion at 37 days. UV irradiation of 1 crystals formed a diradical dimer of 1 as a reactive intermediate, coupling reaction of which afforded a corresponding polymer with a molecular weight of >20 000. When the UV-irradiated 1 crystals were dissolved in a degassed solvent, a 1,1,2,2,9,9,10,10-octa(methoxyethoxycarbonyl)[2.2]paracyclophane is formed and it can react with molecular oxygen in air and/or dissolved oxygen in solvents to afford a peroxide-bridged cyclophane. The molecular packing mode of 1 in the crystals was investigated by X-ray crystal structure analysis, and the low polymerization reactivity of 1 in the solid state and the formation of 1,1,2,2,9,9,10,10-octa(methoxyethoxycarbonyl)[2.2]paracyclophane were discussed on th...

Solid polymer electrolytes are prepared by the combination of a polyether, poly(ethylene oxide) (PEO) or poly(ethylene oxide-co-propylene oxide) (P(EO/PO)), and a polyanionic lithium salt, (poly(lithium sorbate) (Poly(Li-Sorb)) or poly(lithium muconate) (Poly(Li-Muco)), and their ionic conductivities, lithium ion transference number, electrochemical stabilities, thermal properties, and mechanical strength were investigated in the absence and presence of BF3·OEt2. The ionic conductivities of all solid polymer electrolytes were enhanced by one to two orders of magnitude with addition of BF3·OEt2, because the dissociation of lithium ion and carboxylate anion was promoted by complexation with BF3. The lithium ion transference number in these solid polymer electrolytes showed relatively high values of 0.45–0.88, due to the suppression of the transport of the large counter polymeric anion. These solid polymer electrolytes showed good electrochemical and thermal stabilities, and also, the mechanical strength of the solid polymer electrolytes was improved by the function of crystalline poly(lithium carboxylate)s as a sort of filler.

A β-2-methoxyethyl α-3-[tris(trimethylsiloxy)silyl]propyl itaconate (1) was synthesized successfully as a novel amphiphilic itaconate monomer, and its radical homopolymerization and copolymerization with styrene (St) were investigated. The polymerization rate (Rp) is expressed with Rp = k[1]2.73[AIBN]0.51. Overall activation energy in the radical homopolymerization was determined to be 52.9 kJ/mol. The 1 copolymerized with St in bulk in a highly alternating tendency. The Q, e values of the 1 were obtained to be 1.05 and 0.69, respectively, and the 1 was found to be a conjugative and electron-accepting monomer. Membranes containing the 1 unit, prepared by the copolymerization of 1 with N-vinylpyrrolidone (NVP) and by the terpolymerization of 1, NVP, and 2-hydroxyethyl methacrylate, showed higher oxygen permeability than corresponding ones without the 1 unit, and also they have better transparency than membranes containing 3-[tris(trimethylsiloxy)silyl]propyl methacrylate unit.

Novel dissymmetric fumarate monomers (1a–c) having both an alkoxyethyl group such as 2-methoxyethyl (a), 2-(2-methoxyethoxy)ethyl (b), and 2-(2-(2-methoxyethoxy)ethoxy)ethyl (c) and a bulky 3-[tris(trimethylsiloxy)silyl]propyl group were synthesized successfully, and their radical homopolymerizations and copolymerizations with styrene (St) were investigated. Monomer reactivities of the 1a–c in homopolymerizations were enhanced with an increase in the length of alkoxyethyl chains. The enhancement in the reactivity was explained with the suppression of the termination reaction, resulting from the increased steric hindrance induced by an increase in the size of alkoxyethyl chains. Copolymerizations of the 1a–c with St were carried out in bulk in the presence of AIBN at 60 °C, and their copolymerizations proceeded in a highly alternating tendency regardless of alkoxyethyl chain lengths. The Q, e values of the 1a–c were obtained as 0.48, +1.55 for the 1a, 0.66, +1.16 for the 1b, and 0.60, +1.16 for the 1c, respectively, from the terminal model reactivity ratios, and the 1a–c were found to be conjugative, electron-accepting monomers. Membranes containing the 1a unit, prepared by the copolymerization of 1a with N-vinylpyrrolidone (NVP) and terpolymerization of 1a, NVP, and 2-hydroxyethyl methacrylate, have higher oxygen permeability than those containing no 1a unit, and also they have much better transparency compared with the membranes containing 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate unit. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 420–433, 2009