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The Enzymatic Oxidation of GrapheneOxide Gregg P. Kotchey,† Brett L. Allen,† Harindra Vedala,† Naveena Yanamala,‡,¡ì Alexander A. Kapralov,‡Yulia Y. Tyurina,‡ Judith Klein-Seetharaman,¡ì Valerian E. Kagan,‡ and Alexander Star†,*†Department of Chemistry, ‡Department of Environmental and Occupational Health, and ¡ìDepartment of Structural Biology, University of Pittsburgh, Pittsburgh,Pennsylvania, 15260 ABSTRACT Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon;the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (¡«40 ¦ÌM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, ultraviolet-visible, electron paramagneticresonance, Fourier transform infrared s pectroscopy, transmission electron microscopy, atomic force microscopy, sodium dodecyl sulfate-polyacrylamide gel electrophoresis, and gas chromatography-mass spectrometry. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Owing to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors. KEYWORDS: graphene . oxidation . microscopy . peroxidase . field-effect transistor |
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baiqiaoqiao(RXMCDM´ú·¢): ½ð±Ò+15, ¶àлӦÖú£¡ 2015-10-04 20:16:45
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×÷ÕßÃû×Öû·Ò룬Õâ¶«Î÷ûʲô·ÒëµÄ¡£ÖصãÊDZêÌâ¼°ÕªÒª The Enzymatic Oxidation of GrapheneOxide ʯīϩÑõ»¯ÎïµÄø´ÙÑõ»¯ Department of Chemistry, ‡Department of Environmental and Occupational Health, and ¡ìDepartment of Structural Biology, University of Pittsburgh, Pittsburgh,Pennsylvania, 15260 Æ¥×ȱ¤´óѧ£¬½á¹¹ÉúÎïѧ²¿¼°»·¾³ºÍÖ°Òµ½¡¿µ²¿£¬»¯Ñ§Ïµ ±öϦ·¨ÄáÑÇÖÝÆ¥×ȱ¤ 15260 ABSTRACT ÕªÒª Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. ¶þάʯī̼ÊÇÒ»ÖÖ¾ßÓкܶ๤ҵӦÓõÄвÄÁÏ¡£Ñо¿Æä»¯Ñ§ÐÔÖÊÄ¿±êÖØ´ó¡£ Here, we reported a new phenomenon;the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). ±¾Îı¨µÀÁËÒ»ÖÖÐÂÐÂÏÖÏ󣬼´¾À±¸ù¹ýÑõ»¯ÎïøHRP×÷ÓÃʹ£¬µ¥²ãʯī̼µÄø´ÙÑõ»¯¡£ In the presence of low concentrations of hydrogen peroxide (¡«40 ¦ÌM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. µ±¹ýÑõ»¯ÇâŨ¶ÈµÍʱ (¡«40 ¦ÌM)£¬, HRP´ß»¯Ê¯Ä«Ï©Ñõ»¯ÎïµÄÑõ»¯£¬´Ó¶øµ¼ÖÂÆäµ×Ãæ¿Õ¶´µÄÐγɡ£ During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). ͬһʱÆÚµÄ·ÖÎö±íÃ÷£¬ HRP²»ÄÜÑõ»¯»¯Ñ§»¹ÔÐÔʯīϩÑõ»¯Îï (RGO) The enzymatic oxidation was characterized by Raman, ultraviolet-visible, electron paramagneticresonance, Fourier transform infrared s pectroscopy, transmission electron microscopy, atomic force microscopy, sodium dodecyl sulfate-polyacrylamide gel electrophoresis, and gas chromatography-mass spectrometry. ÓÃÀÂü£¬×ÏÍâ¿É¼ûÎüÊÕ£¬µç×Ó˳´Å¹²Õñ£¬¸µÀïÒ¶±ä»»ºìÍâ¹âÆ×£¬Í¸Éäµç×ÓÏÔ΢¾µ·¨£¬Ô×ÓÁ¦ÏÔ΢¾µ£¬¾Û±ûÏ©õ£°·Äý½ºµçÓ¾ÒÔ¼°ÆøÏàÉ«Æ×-ÖÊÆ×À´±íÕ÷ø´ßÑõ»¯¡£ Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. ¼ÆËã¶Ô½ÓÑо¿±íÃ÷£¬HRPÓÅÏȰ󶨵½Ê¯Ä«Ï©Ñõ»¯Îï¼°RGOÁ½Õߵĵ×Ãæ£¬¶ø²»ÊDZßÔµ¡£ Owing to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. ÓÉÓÚʯīϩÑõ»¯ÎïÉÏÓиü¶àµØ¶¯Ì¬ÌØÐÔ£¬ÓëRGOÏà±È£¬ HRPµÄѪºìËØ»îÐÔ²¿Î»¸ü½Ó½üÓÚʯīϩÑõ»¯Îï¡£ We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. ÓùýʹÓó¡Ð§Ó¦¾§Ìå¹Ü²âÁ¿£¬±¾ÎÄ»¹Ñо¿ÁË»¹ÔÖмä²úÎï¼°¶à¿×RGOµÄµç×ÓÌØÐÔ¡£ While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. RGO³ÊÏÖ³öÓëµ¥²ãµÄʯīϩÏàËÆµÄVÐδ«ÈÈÐÔÄÜ£¬ÕâÊÇÓÉÓÚÆäÁã´øÏ¶£¬ÖÂʹhRGOÒòÔÚµÒÀ¿ËµãµÄÕýÏòÎ»ÒÆ¶ø±íÏÖ³öpÐͰ뵼ÌåÐÐΪ¡£ This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors. ÕâÖÖpÐÍÐÐΪÏÔʾ³ö hRGO ¿ÉÒÔ¸ÅÄΪ»¥ÏàÁ¬½ÓʯīϩÄÉÃ×´ø£¬Ò»ÖÖÖÆ×÷TET¸ÐÓ¦Æ÷µÄDZÔÚµÄÓÐÎüÒýÁ¦µÄ²ÄÁÏ¡£ |

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