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Self-Assembled Monolayers of Bi-Functionalized Porphyrins: A Novel Class of Hole-Layer-Coordinating Perovskites and Indium Tin Oxide in Inverted Solar Cells

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Angewandte Chemie 2023年第40期135卷

作者： Chieh-Ming Hung Chi-Lun Mai Chi-Chi Wu Bo-Han Chen Chih-Hsuan Lu Che-Chun Chu Meng-Chuan Wang Prof. Shang-Da Yang Prof. Hsieh-Chih Chen Prof. Chen-Yu Yeh Prof. Pi-Tai Chou Department of Chemistry Center for Emerging Materials and Advanced Devices National Taiwan University 106319 Taipei Taiwan Contribution: Conceptualization (lead) Data curation (lead) Formal analysis (lead) Investigation (lead) Project administration (lead) Writing - original draft (lead) Department of Chemistry i-Center for Advanced Science and Technology (i-CAST) Innovation and Development Center of Sustainable Agriculture (IDCSA) National Chung Hsing University 402202 Taichung Taiwan Contribution: Data curation (supporting) Investigation (supporting) Project administration (equal) Resources (lead) Writing - original draft (lead) Contribution: Software (lead) Institute of Photonics Technologies National Tsing Hua University 300044 Hsinchu Taiwan Contribution: Data curation (lead) Formal analysis (lead) Contribution: Data curation (equal) Formal analysis (equal) Contribution: Data curation (supporting) Formal analysis (supporting) Investigation (supporting) Contribution: Data curation (supporting) Resources (supporting) Contribution: Writing - review & editing (supporting) Department of Chemistry Fu Jen Catholic University 242062 New Taipei City Taiwan Contribution: Writing - original draft (equal) Writing - review & editing (lead) Contribution: Writing - original draft (lead) Writing - review & editing (equal) Contribution: Writing - original draft (supporting) Writing - review & editing (lead)

Self-assembled monolayers (SAMs) offer the advantage of facile interfacial modification, leading to significant improvements in device performance. In this study, we report the design and synthesis of a new series of carboxylic acid-functionalized porphyrin derivatives, namely AC-1, AC-3, and AC-5, and present, for the first time, a strategy to exploit the large π-moiety of porphyrins as a backbone for interfacing the indium tin oxide (ITO) electrode and perovskite active layer in an inverted perovskite solar cell (PSC) configuration. The electron-rich nature of porphyrins facilitates hole transfer and the formation of SAMs, resulting in a dense surface that minimizes defects. Comprehensive spectroscopic and dynamic studies demonstrate that the double-anchored AC-3 and AC-5 enhance SAMs on ITO, passivate the perovskite layer, and function as conduits to facilitate hole transfer, thus significantly boosting the performance of PSCs. The champion inverted PSC employing AC-5 SAM achieves an impressive solar efficiency of 23.19 % with a high fill factor of 84.05 %. This work presents a novel molecular engineering strategy for functionalizing SAMs to tune the energy levels, molecular dipoles, packing orientations to achieve stable and efficient solar performance. Importantly, our comprehensive investigation has unraveled the associated mechanisms, offering valuable insights for future advancements in PSCs.

关键词： Functionalized Porphyrins Hole-Selective Layer Perovskite Solar Cells Self-Assembled Monolayers Transient Absorption Spectroscopy

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Improved Biocompatibility of ePTFE by Ion Beam Implantation

Improved Biocompatibility of ePTFE by Ion Beam Implantation

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The 5th Shanghai International Conference on Biophysics and Molecular biology 第五届上海国际力生物学学术会议(SICBM2011)

作者： Hiroshi Ujiie Yoshiaki Suzuki Rena Ujiie Hiroshi Toita Toshiyuki Tanaka Department of Neurosurgery Tokyo Rosai Hospital Beam Technology TeamAdvanced Development and Supporting CenterRIKEN

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Trial Formation of Artificial Bone by Inkjet Powder-Layered Manufacturing

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International Journal of Automation Technology 2008年第3期2卷 156-161页

作者： Yamazawa, Kenji Anzai, Masahiro Yokota, Hideo Himeno, Ryutaro Suzuki, Hiroshi Narahara, Hiroyuki Suzuki, Shigeki Advanced Engineering Team Advanced Development and Supporting Center RIKEN 2-1 Hirosawa Wako-shi Saitama351-0198 Japan Computational Biomechanics Unit RIKEN 2-1 Hirosawa Wako-shi Saitama351-0198 Japan Faculty of Computer Science and Systems Engineering Kyushu Institute of Technology 680-4 Kawazu Iizuka-shi Fukuoka820-8502 Japan NEXT21 K.K 3-38-1 Hongo Bunkyo-ku Tokyo113-0033 Japan

Artificial bone implants are in relatively simple shapes for use mainly by cutting or manually. To produce a desired bone shape, we used tribasic calcium phosphate bone ash powder as the material and aqueous sodium chondroitin sulfate solution as the binder in inkjet powder-layered manufacturing. In experiments, we reproduced a rabbit femur with a precision of 0.6 mm and a minimum longitudinal hollow shaft 2 mm in diameter based on computed tomography data. We gave the brittle artificial bone a compressive strength of 3 MPa by dipping it in water and binder through its hydrate reaction. © Fuji Technology Press Ltd.

关键词： Sulfur compounds

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development of Die Mold Processing Machine with Multi-Spindles and Axes

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International Journal of Automation Technology 2007年第2期1卷 94-102页

作者： Kitamura, Akihiro Takahashi, Ichiro Anzai, Masahiro Takeuchi, Yoshimi Department of Mechanical Engineering Osaka University 2-1 Yamadaoka Osaka Suita-shi560-0871 Japan Advanced Development and Supporting Center RIKEN 2-1 Hirosawa Saitama Wako-shi351-0198 Japan

Within the high quality Metal Mold Manufacturing industry there is a continuing effort to reduce overall costs and shorten lead time from design to completion. This is particularly true in the Automotive Industry where model change over has become more frequent. The molds required for automotive type three dimensional shaped exteriors and interiors are typically in the range of 2400 mm × 4800 mm and can weigh up to 19 tons. Currently, the processing of these large-scale molds requires the material to be put on the table of a machine tool that has a long travel and a bed length of more than twice the travel. By using large-scale horsepower, low spindle speeds and slow feed rates the mold is generated. The dynamics of this industry led to the development of a truly original, unparalleled machine tool. This multi-head, large-scale mold processing machine was found to feature a 40-50% decrease in the processing time required for mold manufacture. The newly developed machine has a range of 1-4 heads allowing a variety of different curved surfaces to be processed at the same time, on the same mold. The multi-tasking capability of this machine tool results in quality improvement and over all cost reduction. © Fuji Technology Press Ltd.

关键词： Machine tools

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Regioselective carbon-carbon bond formation in proteins with palladium catalysis;New protein chemistry by organometallic chemistry (vol 7, pg 134, 2006)

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CHEMBIOCHEM 2007年第2期8卷 159-159页

作者： Kodama, K. Fukuzawa, S. Nakayama, H. Kigawa, T. Sakamoto, K. Yabuki, T. Matsuda, N. Shirouzu, M. Takio, K. Tachibana, K. Yokoyama, S. Department of Biophysics and Biochemistry School of Science The University of Tokyo 7-3-1 Hongo Bunkyo Tokyo 113-0033 Japan Fax: (+81) 3-5841-8057 Protein Research Group RIKEN Genomic Sciences Center 1-7-22 Suehiro-cho Tsurumi-ku Yokohama 230-0045 Japan Department of Chemistry School of Science The University of Tokyo 7-3-1 Hongo Bunkyo Tokyo 113-0033 Japan Fax: (+81) 3-5841-8059 Biomolecular Characterization Team Advanced Development and Supporting Center RIKEN Wako Institute 2–1 Hirosawa Wako Saitama 351-0033 Japan Protein Research Group RIKEN Genomic Sciences Center 1-7-22 Suehiro-cho Tsurumi-ku Yokohama 230-0045 Japan Department of Biophysics and Biochemistry School of Science The University of Tokyo 7-3-1 Hongo Bunkyo Tokyo 113-0033 Japan Fax: (+81) 3-5841-8057 Protein Research Group RIKEN Genomic Sciences Center 1-7-22 Suehiro-cho Tsurumi-ku Yokohama 230-0045 Japan Protein Research Group RIKEN Genomic Sciences Center 1-7-22 Suehiro-cho Tsurumi-ku Yokohama 230-0045 Japan Protein Research Group RIKEN Genomic Sciences Center 1-7-22 Suehiro-cho Tsurumi-ku Yokohama 230-0045 Japan Protein Research Group RIKEN Genomic Sciences Center 1-7-22 Suehiro-cho Tsurumi-ku Yokohama 230-0045 Japan Highthroughput Factory RIKEN Harima Institute 1-1-1 Kouto Mikazuki Sayo Hyogo 679-5148 Japan Department of Chemistry School of Science The University of Tokyo 7-3-1 Hongo Bunkyo Tokyo 113-0033 Japan Fax: (+81) 3-5841-8059 Department of Biophysics and Biochemistry School of Science The University of Tokyo 7-3-1 Hongo Bunkyo Tokyo 113-0033 Japan Fax: (+81) 3-5841-8057 Protein Research Group RIKEN Genomic Sciences Center 1-7-22 Suehiro-cho Tsurumi-ku Yokohama 230-0045 Japan Highthroughput Factory RIKEN Harima Institute 1-1-1 Kouto Mikazuki Sayo Hyogo 679-5148 Japan

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Tailor-made tricalcium phosphate bone implant directly fabricated by a three-dimensional ink-jet printer

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Journal of Artificial Organs 2006年第4期9卷 234-240页

作者： Igawa, Kazuyo Mochizuki, Manabu Sugimori, Osamu Shimizu, Koutaro Yamazawa, Kenji Kawaguchi, Hiroshi Nakamura, Kozo Takato, Tsuyoshi Nishimura, Ryouhei Suzuki, Shigeki Anzai, Masahiro Chung, Ung-Il Sasaki, Nobuo Division of Tissue Engineering University of Tokyo Hospital Bunkyo-ku Tokyo 113-8655 7-3-1 Hongo Japan Laboratory of Veterinary Diagnostic Imaging Department of Veterinary Medicine Tokyo University of Agriculture and Technology Tokyo Japan Laboratory of Veterinary Surgery Graduate School of Agricultural and Life Sciences University of Tokyo Tokyo Japan New X-national Technology K.K. Tokyo Japan Advanced Development and Supporting Center RIKEN Wako Japan Division of Sensory and Motor System Medicine Faculty of Medicine University of Tokyo Tokyo Japan

Rapid prototyping (RP) is a molding technique that builds a three-dimensional (3D) model from computer-aided design (CAD) data. We fabricated new tailor-made bone implants (TIs) from α-tricalcium phosphate powder using an RP ink-jet printer based on computed tomography (CT) data, and evaluated their safety and efficacy. CT data of the skulls of seven beagle dogs were obtained and converted to CAD data, and bone defects were virtually made in the skull bilaterally. TIs were designed to fit the defects and were fabricated using the 3D ink-jet printer with six horizontal cylindrical holes running through the implants, designed for possible facilitation of vascular invasion and bone regeneration. As a control, hydroxyapatite implants (HIs) were cut manually from porous hydroxyapatite blocks. Then, craniectomy was performed to create real skull defects, and TIs and HIs were implanted. After implantation, CT was performed regularly, and the animals were euthanized at 24 weeks. No major side effects were observed. CT analysis showed narrowing of the cylindrical holes;bony bridging between the implants and the temporal bone was observed only for TIs. Histological analysis revealed substantial new bone formation inside the cylindrical holes in the TIs, while mainly connective tissues invaded the porous structures in HIs. Bone marrow was observed only in TIs. Osteoclasts were seen to resorb regenerated bone from inside the cylindrical holes and to invade and probably resorb the TIs. These data suggest that TIs are a safe and effective bone substitute, possessing osteoconductivity comparable with that of HIs. © 2006 The Japanese Society for Artificial Organs.

关键词： Biodegradability Bone substitute Tailor-made implant Three-dimensional ink-jet printer Tricalcium phosphate

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Evaluation of a novel organic-inorganic hybrid porous membrane

Evaluation of a novel organic-inorganic hybrid porous membra...

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54th SPSJ Annual Meeting 2005

作者： Tezuka, Teppei Nagaoka, Syoji Suzuki, Yoshiaki Iwaki, Masaya Kawakami, Hiroyoshi Dept. of Applied Chemistry Tokyo Metropolitan University Hachioji Tokyo 192-0397 Japan Advanced Development and Supporting Center RIKEN 2-1 Hirosawa Wako Saitama 351-0198 Japan

We report the water permeability and rejection properties of sucrose for a novel organic-inorganic hybrid porous membrane made by combining the ion irradiation and plasma etching. The porous membrane showed both the higher water flux and the rejection property. We demonstrated that the pore size formed on the porous membrane was able to be effectively controlled by the plasma treatment time and the skin layer thickness.

关键词： Polymeric membranes

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Enzymatic degradation of poly(lactide) [II]-AFM analysis

Enzymatic degradation of poly(lactide) [II]-AFM analysis

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54th SPSJ Annual Meeting 2005

作者： Kikkawa, Yoshihiro Yamashita, Koichi Kurokawa, Kenji Kanesato, Masatoshi Doi, Yoshiharu Nanoarchitectonics Research Center National Institute of Advanced Industrial Science and Technology Tsukuba Central 4 1-1-1 Higashi Tsukuba Ibaraki 305-8562 Japan Advanced Development and Supporting Center Polymer Chemistry Laboratory RIKEN Institute 2-1 Hirosawa Wako-shi Saitama 351-0198 Japan Department of Innovative and Engineered Materials Tokyo Institute of Technology 4259 Nagatsuta Midori-ku Yokohama 226-8502 Japan

Direct observation of proteinase K adsorbed onto poly(lactide) (PLA) thin film was performed by using atomic force microscopy (AFM). The amount of proteinase K molecules bound onto the PLA surface was increased with increasing the concentration of enzyme solution. Removing the proteinase K molecules on the PLA surface during enzymatic reaction allowed us to observe the "footprint" of the erosion. AFM result suggests that adsorbed proteinase K molecules moved around on the PLA surface.

关键词： Polymers

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Cover Picture: Regioselective Carbon–Carbon Bond Formation in Proteins with Palladium Catalysis;New Protein Chemistry by Organometallic Chemistry (ChemBioChem 1/2006)

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ChemBioChem 2006年第1期7卷 1-1页

作者： Koichiro Kodama Seketsu Fukuzawa Dr. Hiroshi Nakayama Dr. Takanori Kigawa Dr. Kensaku Sakamoto Dr. Takashi Yabuki Dr. Natsuko Matsuda Mikako Shirouzu Dr. Koji Takio Dr. Kazuo Tachibana Prof. Shigeyuki Yokoyama Prof. Department of Biophysics and Biochemistry School of Science The University of Tokyo 7-3-1 Hongo Bunkyo Tokyo 113-0033 Japan Fax: (+81) 3-5841-8057 Protein Research Group RIKEN Genomic Sciences Center 1-7-22 Suehiro-cho Tsurumi-ku Yokohama 230-0045 Japan Department of Chemistry School of Science The University of Tokyo 7-3-1 Hongo Bunkyo Tokyo 113-0033 Japan Fax: (+81) 3-5841-8059 Biomolecular Characterization Team Advanced Development and Supporting Center RIKEN Wako Institute 2–1 Hirosawa Wako Saitama 351-0033 Japan Highthroughput Factory RIKEN Harima Institute 1-1-1 Kouto Mikazuki Sayo Hyogo 679-5148 Japan

The cover picture shows how the carbon–carbon bond formation in a protein has been achieved by a combined approach of organic synthesis and genetic engineering. Palladium-catalyzed reactions have been used in the synthesis of a wide variety of organic molecules. Among them, the Mizoroki–Heck reaction allows alkenylation of an aryl iodide to be performed under mild conditions. In the article by S. Fukuzawa, K. Tachibana, S. Yokoyama, et al. on p. 134 ff, it is demonstrated how fragile biomolecules like proteins can be substrates for palladium-catalyzed reactions.

关键词： catalysis iodophenylalanine Mizoroki–Heck reaction palladium proteins site-specific functionalization

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Enzymatic degradation of poly(lactide) [I] - QCM analysis

Enzymatic degradation of poly(lactide) [I] - QCM analysis

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54th SPSJ Annual Meeting 2005

作者： Yamashita, Koichi Kikkawa, Yoshihiro Kurokawa, Kenji Kanesato, Masatoshi Doi, Yoshiharu Advanced Development and Supporting Center RIKEN Institute 2-1 Hirosawa Wako-shi Saitama 351-0198 Japan Nanoarchitectonics Research Center National Institute of Advanced Industrial Science and Technology Tsukuba Central 4 1-1-1 Higashi Tsukuba Ibaraki 305-8562 Japan Polymer Chemistry Laboratory RIKEN Institute 2-1 Hirosawa Wako-shi Saitama 351-0198 Japan Department of Innovative and Engineered Materials Tokyo Institute of Technology Midori-ku Yokohama 226-8502 Japan

Enzymatic degradation of the poly(L-lactide) (PLLA) amorphous film by proteinase K was investigated by using a quartz crystal microbalance (QCM) technique. The erosion rate increased with increasing enzyme concentrations and attained to be constant under the condition of [proteinase K] > 100 μg/mL. The amount of the enzyme molecules adsorbed to the film was quantitatively evaluated at various concentrations and it revealed that the erosion rate is determined by the amount of adsorbed enzyme. Adsorption of proteinase K was irreversible despite lack of the binding domain. The hydrophobic interaction between the enzyme and the film surface was suggested to be a dominant interaction for enzyme adsorption.

关键词： Polymers

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