Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 15

1 August 2010

Volume 48, Issue 15

Pages 3217–3500

  1. Articles

    1. Top of page
    2. Articles
    3. Notes
    1. One-pot synthesis of surface-functionalized molecularly imprinted polymer microspheres by iniferter-induced “living” radical precipitation polymerization (pages 3217–3228)

      Junyi Li, Baiyi Zu, Ying Zhang, Xianzhi Guo and Huiqi Zhang

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24057

      Thumbnail image of graphical abstract

      The development of iniferter-induced “living” radical precipitation polymerization and its application in molecular imprinting are described. The new polymerization technique was implemented by introducing iniferter-induced “living” radical polymerization mechanism into precipitation polymerization system, and it has proven to be an general approach for generating both narrow disperse poly(ethylene glycol dimethacrylate) microspheres and molecularly imprinted polymer (MIP) microspheres with obvious molecular imprinting effects towards the templates. In particular, the living nature of ILRPP allows the one-pot synthesis of functional polymer/MIP microspheres with surface-bound iniferter groups, which are highly useful for preparing advanced polymer/MIP materials by their direct controlled surface modification.

    2. Synthesis and characterization of thermoresponsive poly(ethylene glycol)-based hydrogels and their magnetic nanocomposites (pages 3229–3235)

      Samantha A. Meenach, Kimberly W. Anderson and J. Zach Hilt

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24087

      Thumbnail image of graphical abstract

      Poly(ethylene glycol) (PEG)-based hydrogel nanocomposites were fabricated with iron oxide nanoparticles physically entrapped in the hydrogel matrix. The nanocomposites showed temperature-responsive behavior due to the PEG present in the systems and they were able to heat upon exposure to an alternating magnetic field (AMF) due to the presence iron oxide nanoparticles. (a) Shows the temperature-responsive behavior of the nanocomposites upon exposure to an AMF whereas (b) shows the actual deswelling behavior of the gels before and after exposure to the AMF.

    3. Poly[N-isopropyl acrylamide]-co-polyurethane copolymers for controlled release of urea (pages 3236–3243)

      Anu Stella Mathews and Suresh Narine

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24090

      Thumbnail image of graphical abstract

      These SEM images show a urea particle, approximately spherical, normally used as fertilizer; the urea particle coated in a smooth coating of PNIPAm-PU copolymer; and a cross-section of the coated urea particle, showing the uniform nature of the coating. The coating is applied in a simple process by immersing the urea particle in a hot melt of the co-polymer, followed by centrifugation to remove excess co-polymer.

    4. Fully biodegradable polymeric micelles based on hydrophobic- and hydrophilic-functionalized poly(lactide) block copolymers (pages 3244–3254)

      Benjamin Nottelet, Claudia Di Tommaso, Karine Mondon, Robert Gurny and Michael Möller

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24100

      Thumbnail image of graphical abstract

      Fully degradable amphiphilic diblock copolymers obtained from a combination of hydrophobic hexyl-functionalized poly(lactides) with hydrophilic-functional poly(lactides) or poly(malic acid) are reported for the first time. The resulting poly(lactide)-based micelles have diameter below 100 nm and low critical micellar concentrations. After loading of a hydrophobic model compound, micelles in vitro stabilities have been investigated as a function of temperature and pH with regard to their potential use in medical cancer treatment.

    5. Thiol-isocyanate-acrylate ternary networks by selective thiol-click chemistry (pages 3255–3264)

      Hironori Matsushima, Junghwan Shin, Christopher N. Bowman and Charles E. Hoyle

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24102

      Thumbnail image of graphical abstract

      The phosphine-acrylate cocatalyzed thiol-isocyanate coupling reaction was preferentially faster than the thiol-acrylate Michael addition at low-phosphine concentration in the presence of excess acrylate. This novel thiol/isocyanate/acrylate ternary network prepared by sequential thiol-isocyanate and thiol-acrylate Michael Click reactions followed by photopolymerization of residual acrylates achieved a wide range of physical/mechanical properties by simple changes in the component concentrations. Control of the reaction sequence in one pot using selective and preferential thiol Click type reactions provides new opportunities for developing high-performance polymeric materials.

    6. Thermal stability of porous it-PMMA thin film obtained by the extraction of st-PMAA from it-PMMA/st-PMAA stereocomplex with layer-by-layer assembly on a substrate (pages 3265–3270)

      Hiroharu Ajiro, Masumi Maegawa and Mitsuru Akashi

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24103

      Thumbnail image of graphical abstract

      The porous isotactic (it-) poly(methyl methacrylate) (PMMA) film on substrate, which was prepared by layer-by-layer assembly with it-PMMA and syndiotactic (st-) poly(methacrylic acid) (PMAA) and the subsequent extraction of st-PMAA was examined on its thermal stability. Quartz crystal microbalance (QCM), IR, and XRD studies revealed that the porous structure and its functionality as nanospace was retained at 70 °C, however, it-PMAA was crystallized to form double stranded structure and st-PMAA incorporation ability was lost when it was heat up to 90 °C in water.

    7. Synthesis of amphiphilic A3B mikto-arm copolymers from a sugar core: Combination of hydrophobic PCL and hydrophilic glycopolymers for biocompatible nanovector preparation (pages 3271–3280)

      Fabian Suriano, Olivier Coulembier and Philippe Dubois

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24109

      Thumbnail image of graphical abstract

      A3B mikto-arm amphiphilic copolymers composed by three hydrophobic poly(ε-caprolactone) chains and one hydrophilic polysugar segment have been obtained in a control way by applying a seven steps synthesis. The key-step of their preparation relies on the use of a protected sugar as initiator allowing the ring-opening polymerization of the ε-caprolactone and the atom transfer radical polymerization of sugar-based methacrylate monomers. Regarding their composition, those mikto-arm structures have proved amphiphilic and characterized by both low CMCs and hydrodynamic diameters well-suited for drug targeting applications.

    8. Novel soluble fluorinated poly(ether imide)s with different pendant groups: Synthesis, thermal, dielectric, and optical properties (pages 3281–3289)

      Yu Liu, Yan Xing, Yunhe Zhang, Shaowei Guan, Haibo Zhang, Yu Wang, Yongpeng Wang and Zhenhua Jiang

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24111

      Thumbnail image of graphical abstract

      Three series of soluble poly(ether imide)s (PEIs) with excellent thermal stability were prepared by two-step chemical imidization method. Casting films of the PEIs showed high optical transparency as well as high tensile modulus, low dielectric constants, and low water uptakes.

    9. Synthesis and structural characterization of dendritic-linear PMA-APM-r-PS copolymers for a self-assembled microporous matrix (pages 3290–3301)

      Shang-Ju Hsieh, Cheng-Chien Wang and Chuh-Yung Chen

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24113

      Thumbnail image of graphical abstract

      A set of dendritic-linear copolymers, PMA-APM-r-PS, was successfully prepared by copolymerization of the novel dendritic macromonomer, MA-APM, with styrene monomer. The self-assembling behavior can make the submicron phase segregation morphology of the PMA-APM-r-PS copolymer to present a uniform size distribution of ordered-array structures.

    10. Novel long chain unsaturated diisocyanate from fatty acid: Synthesis, characterization, and application in bio-based polyurethane (pages 3302–3310)

      Leila Hojabri, Xiaohua Kong and Suresh S. Narine

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24114

      Thumbnail image of graphical abstract

      Polyurethanes (PUs) form a versatile class of polymers. The synthesis of PU is normally carried out from di- or polyfunctional hydroxycompounds (polyol) with di- or polyfunctional isocyanates, which are usually industrially produced from petroleum. The progressive dwindling of fossil resources has driven research to develop alternatives based on renewable resources for the production of polymer materials. This work demonstrates the possibility of producing long chain linear unsaturated terminal diisocyanate from fatty acid, and the feasibility of utilizing this new diisocyanate for the production of bio-based PUs entirely from natural sources by reacting it with canola diol and canola polyol, respectively.

    11. Facile syntheses, morphologies, and optical absorptions of P3HT coil-rod-coil triblock copolymers (pages 3311–3322)

      Herman Lim, Kuo-Tung Huang, Wei-Fang Su and Chi-Yang Chao

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24115

      Thumbnail image of graphical abstract

      Regioregular P3HT triblock copolymers with well-defined compositions and molecular weights were synthesized from coupling reaction between aldehyde-terminated P3HT and polymeric anions (polystyrene, polyisoprene, and polymethylmethacrylate) in high yield. Photophysical properties of these block copolymers in solid state were found to relate to their morphologies, which were affected by the flexibility of the non-P3HT segment as well as the χ value between P3HT and the non-P3HT segment.

    12. Miktoarm star copolymers via combination of RAFT arm-first technique and aldehyde–aminooxy click reaction (pages 3323–3330)

      Zhao-Mian Wu, Hui Liang, Jiang Lu and Wen-Li Deng

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24116

      Thumbnail image of graphical abstract

      A new route to miktoarm star copolymers with multiple arms has been developed by combining RAFT arm-first method and oxime click chemistry. Star polystyrene with aldehyde functionalized core was prepared through cross-linking of the preformed linear macro-RAFT agents using an aldehyde-containing divinyl compound. The aldehyde groups in the star core were then allowed to simply click with aminooxy-terminated PEGs to form PS-PEG miktoarm star copolymers.

    13. Synthesis and characterization of donor–acceptor poly(3-hexylthiophene) copolymers presenting 1,3,4-oxadiazole units and their application to photovoltaic cells (pages 3331–3339)

      Hsu-Shen Wang, Ming-Shin Su and Kung-Hwa Wei

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24117

      Thumbnail image of graphical abstract

      We have used Grignard metathesis polymerization to prepare poly(3-hexylthiophene)-based copolymers containing electron-withdrawing 4-tert-butylphenyl-1,3,4-oxadiazole-phenyl moieties as side chains. The photocurrents of devices were enhanced in the presence of an optimal amount of the oxadiazole moieties, thereby leading to improved power conversion efficiencies.

    14. Synthesis of polymer microspheres functionalized with chiral ligand by precipitation polymerization and their application to asymmetric transfer hydrogenation (pages 3340–3349)

      Naoki Haraguchi, Akihiro Nishiyama and Shinichi Itsuno

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24118

      Thumbnail image of graphical abstract

      Monodisperse crosslinked poly(divinylbenzene) and poly(methacrylic acid-co-ethylene glycol dimethacrylate) microspheres with (1R,2R)-N1-toluenesulfonyl-1,2-diphenylethylene-1,2-diamine ((R,R)-TsDPEN) moiety were successfully prepared by precipitation polymerization. The functionalized polymer microspheres were applied to asymmetric transfer hydrogenation of ketone and imine. Polymer microsphere-supported chiral catalysts showed good reactivity and enantioselectivity in the reaction. The catalyst could be reused four times without loss of yield and enantioselectivity.

    15. Well-defined pH-sensitive block glycopolymers via reversible addition–fragmentation chain transfer radical polymerization: Synthesis, characterization, and recognition with lectin (pages 3350–3361)

      Li Liu, Jiechun Zhang, Wenhui Lv, Yan Luo and Xiaojuan Wang

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24119

      Thumbnail image of graphical abstract

      pH-Sensitive block glycopolymer poly(2-(diethylamino)ethyl methacrylate)-b-poly(3-O-methacryloy-α,β-D-glucopyranose) (PDEAEMA-b-PMAGlc) was prepared via RAFT polymerization based on the protected glycomonomer 3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-D-glucofuranose (MAIpGlc). PDEAEMA-b-PMAGlc self-assembled into spherical micelles at alkaline pH. The micelles composed of hydrophilic glycopolymer shells with pendant glucose groups and hydrophobic PDEAEMA cores. The glucose-shelled micelles had specific recognition with protein Concanavalin A (Con A).

    16. Poly(lactic acid) brushes grow longer at lower temperatures (pages 3362–3367)

      Lebo Xu and Christopher B. Gorman

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24120

      Thumbnail image of graphical abstract

      PLA brushes grown at room temperature are thicker than brushes grown at higher temperatures.

    17. The spectrophotometric study of a fluorescence-enhanced inclusion complex threaded with β-cyclodextrin: Synthesis and characterization (pages 3368–3374)

      Yi-Hong Chiu and Jui-Hsiang Liu

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24121

      Thumbnail image of graphical abstract

      The enhancement of photo-induced fluorescence is achieved via monomers end-capped with a phenyl-[1,3,4]oxadiazolyl moiety threaded with β-cyclodextrins. Because of a relatively strong host-guest interaction in the inclusion complex, formation of an excimer and emission of UV-vis light occurred effectively. In this case, a smaller distance between the host and guest molecules may favor excimer formation. Host-guest molecules in the inclusion complex can be considered as intramolecular to each other.

    18. Selective single monomer addition in living cationic polymerization: Sequential double end-functionalization in combination with capping agent (pages 3375–3381)

      Shohei Ida, Takaya Terashima, Makoto Ouchi and Mitsuo Sawamoto

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24122

      Thumbnail image of graphical abstract

      We found that di-tert-butyl {N-[2-(vinyloxy)ethyl]imido}dicarboxylate (BocVE) was a unique monomer to induce single addition for living cationic polymerization of NBVE with SnCl4. This would be due to the bulky side chain interacting with the terminal carbocation to block the further propagation. The Boc side chain, introduced at the terminal with a single unit, was quantitatively deprotected into amine, and also the combination with a conventional capping agent (e.g., sodium diethyl malonate) led to sequential double functionalization with, for example, amine and carboxylic acid.

    19. Photoluminescent energy transfer from poly(phenyleneethynylene)s to near-infrared emitting fluorophores (pages 3382–3391)

      Mindy Levine, Inja Song, Trisha L. Andrew, Steven E. Kooi and Timothy M. Swager

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24123

      Thumbnail image of graphical abstract

      Blended thin films were fabricated which contain conjugated fluorescent polymers and near-infrared emitting fluorophores. Highly efficient energy transfer was observed from the polymer to the fluorophore, with nearly two orders of magnitude amplified fluorophore emission observed in the near-infrared spectral region. This amplified emission does not require appreciable spectral overlap between the polymer emission and fluorophore absorption spectra. Our results offer substantial possibilities in the design of highly sensitive turn-on fluorescent sensors with negligible background polymer emission in the spectral region of interest.

    20. Synthesis and properties of new aromatic polyamides with redox-active 2,4-dimethoxytriphenylamine moieties (pages 3392–3401)

      Sheng-Huei Hsiao, Guey-Sheng Liou, Yi-Chun Kung and Tzu-Jung Hsiung

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24124

      Thumbnail image of graphical abstract

      A series of new redox-active polyamides has been prepared from 4,4′-diamino-2″,4″-dimethoxytriphenylamine with various aromatic dicarboxylic acids. Incorporation of 2,4-dimethoxytriphenylamine units to the polymer main chain not only functionalizes the polyamides with stable redox properties but also leads to enhanced solubility and good thin-film formability. Aside from high Tg and Ts values and good thermal stability, the polymers also revealed stable electrochromic properties, changing from colorless neutral state to green and blue-purple oxidized states. The polymer films exhibited high coloration efficiency, high optical contrast ratio, reasonable response times, and long-term redox and electrochromic reversibility.

    21. Cyclic alkoxyamine-initiator tethered by azide/alkyne-“click”-chemistry enabling ring-expansion vinyl polymerization providing macrocyclic polymers (pages 3402–3416)

      Atsushi Narumi, Sylvia Zeidler, Haitham Barqawi, Claudia Enders and Wolfgang H. Binder

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24126

      Thumbnail image of graphical abstract

      A cyclic initiator for the NMP is a powerful tool for demonstrating the ring-expansion “vinyl” polymerizations. For this purpose, we prepared an acyclic NMP-initiator that includes an azide and a terminal alkyne, which is subsequently tethered via an intramolecular azide/alkyne-“click”-reaction, producing the target cyclic NMP-initiator. The polymerizations of styrene with cyclic NMP-initiator were performed and resultant polymers were characterized, proving that cyclic NMP-initiator mediated the ring-expansion polymerization of styrene. Furthermore, radical ring-crossover reactions originating from the exchange of the inherent nitroxides were shown to occur to generate macrocyclic polystyrenes with higher expanded rings.

    22. Hole-transporting host-polymer series consisting of triphenylamine basic structures for phosphorescent polymer light-emitting diodes (pages 3417–3430)

      Manuel W. Thesen, Bianca Höfer, Marc Debeaux, Silvia Janietz, Armin Wedel, Anna Köhler, Hans-Hermann Johannes and Hartmut Krueger

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24127

      Thumbnail image of graphical abstract

      We synthesised a series of novel hole-transporting host-polymers with triphenylamine as a basic structure. The host-polymer systems are fully characterized with regard to electrochemical, optical, and electrooptical properties in blend systems with a green phosphorescent dopant and an electron-transporting molecule. The carbazolyl and phenothiazinyl side-attached polymers with a polystyrene backbone provided the best overall performances as host-matrices in single-layer phosphorescent PLEDs.

    23. Water-soluble hyperbranched polyelectrolytes with high fluorescence quantum yield: Facile synthesis and selective chemosensor for Hg2+ and Cu2+ ions (pages 3431–3439)

      Biqing Bao, Lihui Yuwen, Xiaowei Zhan and Lianhui Wang

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24128

      Thumbnail image of graphical abstract

      A new carboxylic-functionalized and water-soluble hyperbranched polyfluorene HPFA2 has been synthesized via the simple “A2 + B2 + C3” protocol based on Suzuki coupling polymerization. The polymer showed high fluorescence quantum yield (89%) in aqueous media and was also a sensitive and selective sensor for Hg2+ and Cu2+ ions relative to other metal ions.

    24. Thermo-responsive glycopolymer chains grafted onto honeycomb structured porous films via RAFT polymerization as a thermo-dependent switcher for lectin Concanavalin a conjugation (pages 3440–3455)

      Eun Hee Min, S. R. Simon Ting, Laurent Billon and Martina H. Stenzel

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/pola.24129

      Thumbnail image of graphical abstract

      Thermo-responsive glycopolymers were grafted from a crosslinked honeycomb structured porous film using the RAFT process. The interaction between the glycopolymers and Concanavalin A were switched on and off depending on the temperature.

    25. Stereoisomeric effects in thermo-remendable polymer networks based on Diels–Alder crosslink reactions (pages 3456–3467)

      Judit Canadell, Hartmut Fischer, Gijsbertus De With and Rolf A. T. M. van Benthem

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24134

      Thumbnail image of graphical abstract

      This article describes the synthesis, the spectroscopic, and the thermal characterization of linear and crosslinked polymers as well as a number of corresponding model compounds, containing Diels-Alder adducts derived from furan and maleimide groups. The thermal reversibility of the DA adducts were studied by differential scanning calorimetry, where possible in combination with 1H NMR spectroscopy. It was established that the endo and exo DA stereoisomers show significantly different thermal responses: the rDA of the endo DA-adducts typically takes place at 20–40 K lower temperatures than that of the corresponding exo DA-adducts.

    26. Multistimuli responsive micelles based on well-defined amphiphilic comb poly(ether amine) (acPEA) (pages 3468–3475)

      Chunfeng Di, Xuesong Jiang, Rui Lui and Jie Yin

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24135

      Thumbnail image of graphical abstract

      A series of well-defined amphiphilic comb poly(ether amine)s (acPEA)s were successfully synthesized. These acPEAs can self-assemble into stable nanomicelles, whose aggregation is responsive to temperature, pH, and ionic strength with tunable cloud point (CP).

    27. Synthesis, characterization, and properties of amphiphilic chitosan copolymers with mixed side chains by click chemistry (pages 3476–3486)

      Weizhong Yuan, Zhengda Zhao, Shuying Gu and Jie Ren

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24136

      Thumbnail image of graphical abstract

      Amphiphilic chitosan copolymers with mixed side chains (CS-g-PCL/PEO) were synthesized by “graft to” approach via click chemistry. The melting and crystallization behaviors, crystalline morphology, and hydrophilicity of CS-g-PCL/PEO copolymers can be adjusted by the alteration of the feed ratio of PCL and PEO segments. Moreover, the CS copolymers can self-assemble into spherical micelles in aqueous solution. Investigation shows that size of CS copolymer micelles increased with the increase of the content of hydrophobic PCL segments in copolymers.

    28. Synthesis, characterization, and aqueous self-assembly of amphiphilic poly(ethylene oxide)-functionalized hyperbranched fluoropolymers (pages 3487–3496)

      Wenjun Du, Yali Li, Andreas M. Nyström, Chong Cheng and Karen L. Wooley

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/pola.24149

      Thumbnail image of graphical abstract

      Complex, amphiphilic polymers were synthesized via core-first polymerization of inimer 1-(4′-(bromomethyl)benzyloxy)-2,3,5,6-tetrafluoro-4-vinylbenzene by atom transfer radical self-condensing vinyl polymerization (ATR-SCVP) followed by substitution of the halides with poly(ethylene oxide) amine (PEO-NH2) in different grafting numbers and chain lengths to afford PEO-functionalized HBFPs [(PEOx)y-HBFPs]. As determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) experiments, these amphiphilic polymers readily formed nanosized micelles of 12–28 nm in aqueous solution. Furthermore, the micelles displayed aggregation behaviors that could be mediated by the numbers and lengths of the PEO units.

  2. Notes

    1. Top of page
    2. Articles
    3. Notes
    1. You have free access to this content
      Synthesis and polymerization of novel fluoroalkyl 2-trifluoromethylacrylate possessing tetrahydrofuran moiety (pages 3497–3500)

      Akihiro Hosoya, Hiroshi Hamana and Tadashi Narita

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/pola.24110

      Thumbnail image of graphical abstract

      Synthesis and polymerization of novel fluoroalkyl 2-trifluoromethylacrylate [CH2[DOUBLE BOND]C(CF3)COOCH(CF3)CF2(C4H7O)] were developed. The fluorinated alcohol was derived by hydrolysis of the product from the radical addition of 2-benzoxypentafluoropropene [CF2[DOUBLE BOND]C(CF3)OCOC6H5] with tetrahydrofuran. Novel fluoroalkyl 2-trifluoromethylacrylate was synthesized by the reaction of 2-trifluoromethylacryloyl chloride with the fluorinated alcohol to yield 1,1,3,3,3-pentafluoro-1-(2-tetrahydrofuranyl)-2-propyl trifluoromethylacrylate. Radical and anionic polymerization of the monomer were examined to afford a polymer of 1.1 × 104 as the highest molecular weight initiated by benzoyl peroxide at 60 °C despite low yield of the polymer although the average molecular weight of whole products was limited to about 2 × 103.

SEARCH

SEARCH BY CITATION