Special Issue Organo-Fluorine Chemical Science Inventing the Fluorine Future 2012 Helmut Martin Hugel¨ (Ed.) MDPI OPEN ACCESS External Editors Editorial Office Editor-in-Chief MDPI AG Prof. Dr. Takayoshi Kobayashi Kandererstrasse 25 Advanced Ultrafast Laser Research Center Basel, Switzerland The University of Electro-Communications Phone: +41 61 683 77 34 1-5-1, Chofugaoka, Chofu Website: http://www.mdpi.com/journal/applsci/ Tokyo 182-8585, Japan E-Mail: [email protected] Phone: +81 42 443 5845 Website: http://femto.pc.uec.ac.jp Publisher E-Mail: [email protected] Dr. Shu-Kun Lin Guest Editor Production Editor Dr. Helmut Martin Hugel¨ Dr. Brietta Pike School of Applied Sciences (Chemistry) RMIT University Managing Editor Melbourne VIC 3001 Dr. Ophelia Han PO Box 2476V, Australia Phone: +61 3 99252626 E-Mail: [email protected] Cover picture: Available online at: www.emsl.pnl.gov/upload/1337721062386/ buildingItBetter web.jpg Image credit to: EMSL ISBN 3-906980-33-2 Summary Dear Colleagues, The unique properties imparted on molecules by fluorine substitution, continues to be the subject of intense research as the products have widespread application in all areas of science. Incorporation of fluorine can productively and unpredictably modulate several properties that interest medicinal chemists. Selected drugs for the treatment of high cholesterol such as Lipitor R by Pfizer, Crestor R by AstraZeneca, Zetia R by Merck/Schering-Plough and Lescol R by Novartis all of which contain one or more fluorine atoms that increase metabolic stability, rank amongst the highest selling prescription drugs ever developed. Without doubt every current drug discovery and development program includes and evaluates fluorine-containing drug candidates. A one step 18F-labeling of peptides that contain a specific arene group has emerged that is rapid and simple to perform for 18F PET (positron emission tomography) an in vivo imaging technology for medical use has potential wide application. The synthesis of many pharmaceuticals and agrochemicals with fluorine atoms or groups is closely dependent on the development of new chemical methodologies by organic and industrial chemists. Monofluoroalkenes are known as nonisomerable, nonhydrolyzable stable bioisosteres of amide bonds and recently published highly enantio- and diastereoselective organocatalytic monofluorovinylations reactions have led to the isolation of monofluorovinylated products. A practical methodology for the enatioselective a-fluorination of ketene enolates has been optimized by the utilization of a three-component catalysis system provides an array of a-fluorocarboxylic acid derivatives. A generally useful coupling protocol for copper-catalyzed 1H−perfluoroalkane arylation by aryl iodides allows ready access to a range of perfluoroalkyl substituted aromatic compounds. Tetrafluoroethylene (TFE) is the organofluorine feedstock for the production of poly-(tetrafluoroethylene)polymers that have many applications. The transformation of TFE to a,b,b,-trifluorostyrenes via palladium-catalyzed coupling and arylzincs has been achieved in excellent yields and paves the way to new fluorine-polymers. The deployment of a fluorine substituted conjugated polymer in photovoltaic cells exhibited medium band gap yields above 7% attributed in part to the increased hole mobility of the fluorinated polymer. Organo-fluorine chemistry has had an enormous global impact on science and society, the fluorine fever continues to flourish and grow and we are delighted that experts in this field have agreed to contribute their research achievements to this special issue. Dr. Helmut Martin Hugel¨ Guest Editor Table of Contents Article Nanoimprint Resist Material Containing Ultraviolet Reactive Fluorine Surfactant for Defect Reduction in Lithographic Fabrication Satoshi Takei and Atsushi Sekiguchi, Appl. Sci. 2012, 2, 24-34; doi:10.3390/app2010024 . 1 Review Enhancement of Brillouin Scattering Signal in Perfluorinated Graded-Index Polymer Optical Fibers Yosuke Mizuno and Kentaro Nakamura, Appl. Sci. 2012, 2, 46-60; doi:10.3390/app2010046 . 12 Article Novel Fluorinated Indanone, Tetralone and Naphthone Derivatives: Synthesis and Unique Structural Features Joseph C. Sloop, Paul D. Boyle, Augustus W. Fountain, Cristina Gomez, James L. Jackson, William F. Pearman, Robert D. Schmidt and Jonathan Weyand, Appl. Sci. 2012, 2, 61-99; doi:10.3390/app2010061 . 27 Article A Study of Fluorinated β-Nitrostyrenes as Antimicrobial Agents King Lo, Hugh Cornell, Gina Nicoletti, Neale Jackson and Helmut Hugel,¨ Appl. Sci. 2012, 2, 114-128; doi:10.3390/app2010114 . 66 Article Computational Study on the Acid Catalyzed Reactions of Fluorine-Containing 2,4-Dialkoxy- 3,4-dihydro-2H-pyrans with Aromatic Compounds Norio Ota, Yasuhiro Kamitori, Ryusuke Shirai, Mizuki Hatakenaka and Etsuji Okada, Appl. Sci. 2012, 2, 129-138; doi:10.3390/app2010129 . 81 Article Self-Assembled Fluorinated Organogelators for Surface Modification Anilkumar Raghavanpillai and Vincent A. Franco, Appl. Sci. 2012, 2, 175-191; doi:10.3390/app2010175 . 91 Article Stain Resistance of Cotton Fabrics before and after Finishing with Admicellar Polymerization Srinivas Hanumansetty, Jayanta Maity, Rod Foster and Edgar A. O’Rear, Appl. Sci. 2012, 2, 192-205; doi:10.3390/app2010192 . 108 Review Oxyfluoride Chemistry of Layered Perovskite Compounds Yoshihiro Tsujimoto, Kazunari Yamaura and Eiji Takayama-Muromachi, Appl. Sci. 2012, 2, 206-219; doi:10.3390/app2010206 . 122 Article Optimization of Fluorine Plasma Treatment for Interface Improvement on HfO2/In0:53Ga0:47As MOSFETs Yen-Ting Chen, Yanzhen Wang, Fei Xue, Fei Zhou and Jack C. Lee, Appl. Sci. 2012, 2, 233-244; doi:10.3390/app2010233 . 136 Review Nucleic Acid Based Fluorinated Derivatives: New Tools for Biomedical Applications Christel Dolain, Amit Patwa, Guilhem Godeau and Philippe Barthel´ emy,´ Appl. Sci. 2012, 2, 245-259; doi:10.3390/app2020245 . 148 Review Silicon-[18F]Fluorine Radiochemistry: Basics, Applications and Challenges Carmen Wangler,¨ Alexey Kostikov, Jun Zhu, Joshua Chin, Bjorn¨ Wangler¨ and Ralf Schirrma- cher, Appl. Sci. 2012, 2, 277-302; doi:10.3390/app2020277 . 163 Article Application of Liquid-Phase Direct Fluorination: Novel Synthetic Methods for a Polyfluorinated Coating Material and a Monomer of a Perfluorinated Polymer Electrolyte Membrane Takashi Okazoe, Daisuke Shirakawa and Koichi Murata, Appl. Sci. 2012, 2, 327-341; doi:10.3390/app2020327 . 189 Review An Environmentally Friendly Class of Fluoropolyether: α,!-Dialkoxyfluoropolyethers Menghua Wu, Walter Navarrini, Gianfranco Spataro, Francesco Venturini and Maurizio Sansotera, Appl. Sci. 2012, 2, 351-367; doi:10.3390/app2020351 . 204 Article Synthesis of Some New Fluorinated Hexahydroquinoline and Acridinedione Derivatives in Trifluoroethanol Cosmas O. Okoro, Mumiye A. Ogunwale and Tasneem Siddiquee, Appl. Sci. 2012, 2, 368-374; doi:10.3390/app2020368 . 221 Article Further Successes of the Meisenheimer Model Jon Baker Baker and Max Muir, Appl. Sci. 2012, 2, 443-452; doi:10.3390/app2020443 . 228 Article Fluorine Based Superhydrophobic Coatings Jean-Denis Brassard, D.K. Sarkar and Jean Perron, Appl. Sci. 2012, 2, 453-464; doi:10.3390/app2020453 . 238 Review Overview of the Development of the Fluoropolymer Industry Hongxiang Teng, Appl. Sci. 2012, 2, 496-512; doi:10.3390/app2020496 . 250 Editorial Special Feature Organo-Fluorine Chemical Science Helmut Martin Hugel¨ and Neale Jackson, Appl. Sci. 2012, 2, 558-565; doi:10.3390/app2020558 . 267 Reprinted from Applied Sciences. Cite as: Takei, S.; Sekiguchi, A. Nanoimprint Resist Material Containing Ultraviolet Reactive Fluorine Surfactant for Defect Reduction in Lithographic Fabrication. Appl. Sci. 2012, 2, 24-34; doi:10.3390/app2010024. G Appl. Sci. 2012, 2, 24-34; doi:10.3390/app2010024 OPEN ACCESS applied sciences ISSN 2076-3417 www.mdpi.com/journal/applsci Article Nanoimprint Resist Material Containing Ultraviolet Reactive Fluorine Surfactant for Defect Reduction in Lithographic Fabrication Satoshi Takei 1,2,* and Atsushi Sekiguchi 1 1 Department of Mechanical Systems Engineering, Toyama Prefectural University, Imizu, Toyama 939-0398, Japan 2 Department of Materials Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +81-766-56-7500; Fax: +81-766-56-6131. Received: 9 December 2011; in revised form: 4 January 2012 / Accepted: 5 January 2012 / Published: 16 January 2012 Abstract: The generated resist based defects on the template in addition to the presence of particles and contaminants is critical for ultraviolet curing of nanoimprint lithographic fabrication. This procedure is proven to be suitable for advanced resist material design under the process conditions. Nanoimprint resist material containing an ultraviolet reactive fluorine surfactant was developed to modify the fundamental surface interactions between resists and the template for defect reduction in nanoimprint patterning replication. The developed acrylate type nanoimprint resist material containing 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-hydroxyundecyl acrylate as an ultraviolet reactive fluorine surfactant, indicated excellent patterning dimensional accuracy by minimizing surface free energy, and having the effect of improving the generated resist based defect numbers on the template, with a 500 nm contact hole and 2 μm line patterns, in the replication of 20 nanoimprint process cycles. This desirable concept using an ultraviolet