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5 AVANCE300, 500, 500T 54 HYPERION (NanoFrontier eld) 58 FV-1000D 60 CCD SMART APEX ULTRA X 72 PCR FV1000-D GFPH1 Mitotracker Red 1mol/L OPTIMA 5300DV Hyperion3000

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8 Molecular Analysis & Life Science Center MaLS FORUM Vol.1 Vol Comprehensive Analysis Center for Science, Saitama University 3

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11 30 Department of Chemistry Masaichi SAITO NMR X Faraday 1865 Kekulé (1) (2) (Chart 1) 2000 M Li Li Li R R R R R R R R Si Si Si Si Ge Si R R R R R H R Et Si Ge Ph Et M M M=Li, Na, K M=Li, K Chart 1 2. (a) 1 (3) 2 6

12 2 (4) (Scheme 1) Ph Ph Ph Ph Li Ph Li (excess) Ph Ph Sn Et 2 O/reflux Sn 2PhLi Ph Li 1 2 Scheme 1 2 Ph Ph 2X2(Figure 1)2 2 (4b) Li 1.446(6) Å C(3) C(4) 2.166(4) Å 1.442(5) Å Sn Li Sn C(2) 1.422(6) Å C(1) 2.179(4) Å Figure 1 2 ORTEP ( 40%) (b) ,2-3 (5) (Scheme 2)1.3 1,3-4 (6) (Scheme 2)34 2 Ph Ph Ph Ph Ph Ph Ph Li Sn Ph Ph Ph Sn Ph Sn Ph Li O 2 (1.3 eq) Li (excess) 2 O 2 (1 eq) Li (excess) Ph Li Sn Ph Ph Sn Li Ph Ph 4 Ph Scheme 2 2 Ph 3 Ph 7

13 (c) 5 (7) 6 (8) (Scheme 3) Ph Ph Ph Ph Li Ph 1) Li, cat Naph /Et 2 O Pb Ph 2) DME Ph Pb Ph Li 5 6 Ph Ph Scheme (Figure 2)6 6 (8) 1.412(6) Å C(4) 2.265(5)Å Li C(3) Li 1.431(6) Å C(2) Pb Pb 1.410(6) Å C(1) 2.242(4) Å Figure 2 6 ORTEP ( 40%) ( 5. (1) Joo, W-C.; Hong, J-H.; Choi, S-B.; Son, H-E.; Kim, C. H. J. Organomet. Chem. 1990, 391, 27. (2) For a review, see: Saito, M.; Yoshioka, M. Coord. Chem. Rev. 2005, 249, 765. (3) Saito, M.; Haga, R.; Yoshioka, M. Heteroatom Chem. 2001, 15,

14 (4) (a) Saito, M.; Haga, R.; Yoshioka, M. Chem. Commun. 2002, (b) Saito, M.; Haga, R.; Yoshioka, M.; Ishimura, K.; Nagase, S. Angew. Chem., Int. Ed. 2005, 44, (5) Haga, R.; Saito, M.; Yoshioka, M. J. Am. Chem. Soc. 2006, 128, (6) Haga, R.; Saito, M.; Yoshioka, M. Chem. Eur. J. 2008, 14, (7) Saito, M.; Sakaguchi, M.; Tajima, T.; Ishimura, K.; Nagase, S. Phosphorus Sulfur Silicon Relat. Elem. 2010, 185, (8) Saito, M.; Sakaguchi, M.; Tajima, T.; Ishimura, K.; Nagase, S.; Hada, M. Science 2010, 328,

15 30 Structural and Morphological Approach to the Synthesis of Functional Inorganic Materials Department of Applied Chemistry Hidehiko KOBAYASHI (CsAlSi 2 O 6 ) (CsAlSi 2 O 6 ) ( Ia-3d) K SiO 4 AlO - 4 SiO 4 AlO Fig.1 SiO 4 AlO W ( ) 48 S (24c 24d) 10 Cs + ion (Al,Si)O 4 tetrahedra Fig.1 The lower half of the cell structure of pollucite.

16 Cs-Cs 1-x Al 1-x Si 2+x O 6, Na-Cs 1.0 Na x Al 1+x Si 2-x O 6, Na-Cs 1-x Na x AlSi 2 O 6, XRD RT-1173K (1) Cs-(Cs 1-x Al 1-x Si 2+x O 6 )Na- (Cs 1.0 Na x Al 1+x Si 2-x O 6 ) Na-(Cs 1-x Na x AlSi 2 O 6 ) (Cs + Na + ) Al/(Si+Al) K ( CTE) 1) Cs- Cs +,(RT) 473K RT 1173K Cs CTE Al/(Si+Al) 2 Cs- 2) Na- Na-Cs 1.0 Na x Al 1+x Si 2-x O 6 Cs + Al/(Si+Al) AlO - 4 S Na + CsAlSi 2 O 6 RT 473K 473K 2 Na + 473K Na- CTE Cs-Al/(Si+Al) Na- S Na + Na + Al/(Si+Al) Na- CTE Al/(Si+Al) 3) Na- Na 473K Na (CsAlSi 2 O 6 ) () SiO 4 AlO - 4 Na- CTE Na-Al/(Si+Al) Cs + Na + Al/(Si+Al) 11

17 (2) (Cs +, Na + ) CTE Al/(Si+Al) Fig.2 Cs- ()CTENa- ()Na- () Al/(Si+Al)Cs- Na-() CTE Al/(Si+Al) CTE Al/(Si+Al), Na + Na + Cs + Fig. CTE( K) of the Cs-deficient pollucite(), Na-introduced pollucite(), Na-substituted pollucite with low thermal expansion() and Na-substituted pollucite (Cs +, Na + ) Fig.3(a)-(e) with template thermal expansion() as a function of the Al/(Si+Al) ratio. CsAlSi 2 O 6 Fig.3(a) 16 W Cs + S 2 24 Cs- Cs 1-x Al 1-x Si 2+x O 6 Cs + Fig.3(b) W Na- Cs 1.0 Na x Al 1+x Si 2-x O 6 W Cs + Na + Cs + S (Fig.3(c))Na- Cs 1-x Na x AlSi 2 O 6 Cs + Na + W Na + S Cs + Na + Na- (a) (c) (b) (d) Na + 3(d) Na-Cs + Fig.3 Schematic illustrations of the model for pollucite compounds S Cs + (a):stoichiometric pollucite, (b):cs-deficient pollucite, (c):na-introduced pollucite, W Cs- (d):na-substituted pollucite with low thermal expansion, W (e):na-substituted pollucite with template thermal expansion. Na- Na + W S (e) W CTE (Cs +, Na + ) Al/(Si+Al)Na + Cs + (1+(S site occupancy/w site occupancy )[Al/(Si+Al)](1+S site occupancy/w site occupancy)(cs- Na-, Na-)Fig.4 CTE( K)(R 2 =0.9931) CTE( K) Al/(Si+Al)Cs + Na + 12

18 Cs1-xAl1-xSi2+xO6 Cs1-xNaxAlSi2O6 [Al/(Si+Al)](1+ S site Cs1.0NaxAl1+xSi2-xO6 Cs0.7Na0.2Al0.9Si2.2O6 occupancy/w site occupancy) CTE R 2 = Fig. 4 Relationship between new parameter : [Al/(Si+Al)] (1+Na/Cs) and CTE for various pollucite compounds () // (1) AgTEM(Fig.5) 3nm7nm Ag PtAuCu Ni 3nm5nm TEM Fig. 5 Transmission electron microscopy (TEM) image of Ag nanosized particle 13

19 (2) Ag/Cu (Fig.6) Ag/Cu EDX Ag (Fig.7) Cu (Fig.8) TEM Ag Cu Ag/Cu Ag/Cu EDS Ag/Cu Ag Cu Ag/Cu Cu Ag CuAg Cu Ag Ag/Cu Fig. 6 Transmission electron microscopy (TEM) image of Ag/Cu nanosized particles Fig. 7 Energy dispersive X-ray (EDX) image of the distribution of Ag on Ag/Cu nanosized particles Fig. 8 Energy dispersive X-ray (EDX) image of the distribution of Cu on Ag/Cu nanosized particles (3) (Ni-Co) Ni 2.3nm Co 2.1nm Ni-Co Ni Co TEM Ni Co Fig.9 TEM Ni Fig.10 Co Fig.11 Ni Co Fig.9 TEM 10 Co Ni EDS Co- Ni-Co Ni Co Ni Co Ni-Co 14

20 Fig. 9 Transmission electron microscopy (TEM) image of Ni+Co nano particles. Microwave: 30 min. Fig. 10 Energy dispersive X-ray (EDX) image of the distribution of Ni on Ni+Co nano particles. Fig. 11 Energy dispersive X-ray (EDX) image of the distribution of Co on Ni+Co nano particles B 4 C B 4 C B 4 C B 2 O 3 2B 2 O 3 +7CB 4 C+6CO 2000 B 4 C 2 B-C 1000 B 4 C B-O-C B-C PVA B 4 C B-O-C B 4 C PVAB 4 CPVA B-O-C B 4 C PVATG PVA FT-IR 15

21 B-O-C B 2 O 3 SEM Fig.12 SEM B 2 O 3 : B4C : C Ar B 4 C 1100Fig o C h 5h B 4 C 1150 o C 1100 o C h 1050 o C 1m B 4 C (deg.) Fig.12 SEM image of precursor powder pyrolyzedat 250 o C for 2 h then 600 o C for 2 h in air after removal of B2O3 by washing in hot water (H 2 PtCl 6 ) Fig.14 Pt Pt/Ti SiO 2 H 2 PtCl 6 SiO 2 (Pt,SiO 2 )/Ti Fig.14 Pt IrO 2 Pt (IrO 2,Pt)/Ti1.0M H 2 SO 4 (CV ) Pt Pt-O 16 Intensity (arb. unit) Fig.13 XRD patterns of products by heat treatment at o C for 2 h in Ar flow.

22 (1) (Pt,SiO 2 )/Ti (Pt,SiO 2 )/Ti SEM Fig Pt Pt/Ti SiO 2 (Pt,SiO 2 )/Ti Pt SiO 2 Pt SiO 2 Pt SiO 2 Pt SiO 2 Pt SiO 2 Pt SiO 2 () Pt Pt Pt 1.0,1.2, 1.6mg 0.8,1.0,1.2mg (Pt,SiO 2 )/Ti Pt-O Pt SiO 2 ( ) Fig.14 Surface morphology of Pt/Ti electrode Fig.15 Surface morphology of (Pt, SiO 2)/Ti electrode (2) (IrO 2,Pt)/Ti (IrO 2,Pt)/Ti SEM Fig (IrO 2,Pt)/Ti Pt/Ti Pt 3 IrO 2 (IrO 2,Pt)/Ti CV IrO 2 2 IrO 2 (CsAlSi 2 O 6 ) 16 W () 48 S (24c 24d) Fig.16 Surface morphology of IrO 2,Pt )/Ti electrode 17

23 (B)(C)(N) 18

24 X (NMR) (MS)IR X X NMR X 30 X 2,3- SSe 77 Se 7.6 NMR NMR S 3/2 NMR MS ) X MXC18K 2, ) -S-S(=O)-S(=O)-S- NMR 1 H- 13 C-NMR IR (S=O) X 1-Ad t-bu S S S S 1 1- Ad = 1-1-Ad t-bu S S S S 3 O O 10 C Scheme 1 1-Ad t-bu S O S Ad t-bu S S O 19

25 1. 2,3-3 2,3-3 -S-S(=O)-S(=O)-S--S(=O)-S(=O)- vic-vic- = vicinal 3) 3 vic- 2,3-3 -S(=O)-S(=O)- vic- 1,2,4-1,2-4 4) 5 5) 6 5) syn- 7 6) 1,2-8 7) X (2) Å (1) Å Å Ph O 1-Ad S S S Ph O 1-Ad Ph O t-bu S S S t-bu O Ph Ph S S t-bu S O t-bu O Ph O S S O 1-Ad t-bu O S S O S 2 O S 2 O 50 3 S 2 O 1,3-2 8) R R O S O R S 1-Ad S S R t-bu S S [S 2 O] R S O 3 2 R N 2 S R' R' O Scheme 2 S 2 O S 2 O S 8 S 8 O 2 20

26 8) S 8 O 9 cis- trans ,9) ) 10 S 3 12 S 2 O S 3 SO 2 S 8 O NMR X 9) 12 LiAlH S S O 9 10 S 8 O Scheme 3 H H 12 S S S LiAlH 4 H H 13 SH SH 13 trans-13 C 2 trans-13 trans-13 10) cis- trans ) trans [OSSO] 17 Zr(CH 2 Ph) 4 C B(C 6 F 5 ) 3 (Ph 3 C)[B(C 6 F 5 ) 4 ] Zr 1- (1-) 12) OH t-bu Br 2 t-bu 16 S trans-13 S t-bu t-bu OH Zr(CH 2 Ph) 4 OH S t-bu S t-bu t-bu O CH 2 Ph Zr CH 2 Ph O t-bu t-bu 21 t-bu Scheme 5

27 2,3-3 MS 1. (a) A. Ishii, T. Akazawa, M.-X. Ding, T. Honjo, J. Nakayama, M. Hoshino, M. Shiro, J. Am. Chem. Soc., 115, 4914 (1993). (b) 55, 897 (1997). 2. A. Ishii, M. Nakabayashi, J. Nakayama, J. Am. Chem. Soc., 121, 7959 (1999) , 395 (2006). 4. H. Oshida, A. Ishii, J. Nakayama, Tetrahedron Lett., 43, 5033 (2002). 5. H. Oshida, A. Ishii, J. Nakayama, J. Org. Chem., 69, 1695 (2004). 6. A. Ishii, S. Kashiura, H. Oshida, J. Nakayama, Org. Lett., 6, 2623 (2004). 7. A. Ishii, M. Ohishi, K. Matsumoto, T. Takayanagi, Org. Lett., 8, 91 (2006). 8. A. Ishii, T. Kawai, K. Tekura, H. Oshida, J. Nakayama, Angew. Chem. Int. Ed., 40, 1924 (2001). 9. (a) A. Ishii, M. Suzuki, R. Yamashita, Tetrahedron, 62, 5441 (2006). (b) A. Ishii, M. Suzuki, T. Sone, N. Nakata, Phosphorus, Sulfur, Silicon, 184, 1184 (2009). 10. A. Ishii, A. Ono, N. Nakata, J. Sulf. Chem., 30, 236 (2009). 11. N. Nakata, M. Sakashita, C. Komatsubara, A. Ishii, Eur. J. Inorg. Chem., 447 (2010). 12. A. Ishii, T. Toda, N. Nakata, T. Matsuo, J. Am. Chem. Soc., 131, (2009). 22

28 Soft magnetic granular thin films with the plasma polymerized non-magnetic matrix Department of Functional Materiasl Science Koichi KAKIZAKIKenji KAMISHIMANobuyuki HIRATSUKA Abstract In this review a method for polymerization of fluorocarbon gas in argon plasma to obtain a novel granular structure was reportedwe prepared granular films where FeCo fine particles were distributed in plasma-polymerized fluorocarbon matrix by a facing-targets rf magnetron sputtering methodand investigated the correlation between their structures and magnetic propertiesthe magnetization of the films prepared with the partial pressure of fluorocarbon gas between 0 and 1.0 mtorr decreasedbecause the FeCo content in a unit volume of a film decreasedhoweverthe coercivity of the films decreased drastically with increasing the partial pressure of fluorocarbon gas above 0.4 mtorr This is because the magnetic anisotropy of FeCo particles is decreased by the decrease of grain sizeit was confirmed by a HR-SEM observation that the FeCo-(C 4 F 8 ) n films had the granular structure which was constituted by the very fine FeCo particles and the plasma-polymerized fluorocarbon matrix. IT RFIDRadio Frequency IDentficationRFID MHz MHz 2.45 GHz 1) 2) Fe:70at.%Co:30at.% 23

29 SiO 2 ZrO 2 substrate 3) plasma F Fe, Co Fig1 C 4 F 8 Ar + C 4 F 8 Fe Co Fe 70 Co 30 Fig. 1 Scheme of deposition of the FeCo-(C 4 F 8 ) n granular thin films. 1. rf 99.9% Co 99.99% Fe Fe 70 Co Torr Ar C 4 F mtorr C 4 F 8 C 4 F mtorr 0.49 W/cm nm ( S-4100) X ( Ultima-III)( TM-VSM HGC) 2 4 X 2. Fig.. 2 C 4 F 8 FeCo-(C 4 F 8 ) n SEM C 4 F 8 FeCo 50 nm C 4 F 8 FeCo-(C 4 F 8 ) n FeCo C 4 F 8 FeCo FeCo Fig. 3 C 4 F 8 FeCo-(C 4 F 8 ) n X C 4 F 8 Fig. 2 Surface HR-SEM images for the FeCo-(C 4 F 8 ) n granular thin films prepared with the various partial pressure of fluorocarbon gas. FeCo bcc-feco (1 1 0)FeCo Fe 70 Co 30 bcc bcc (1 1 0) rf FeCo (1 1 0) 24

30 C 4 F 8 FeCo FeCo Fig4 FeCo (M s ) (H ce H ch ) C 4 F 8 C 4 F 8 PC 4 F 8 =0.6 mtorr 1000 emu/cm 3 C 4 F 8 FeCo C 4 F 8 4) Fig5 FeCo-(C 4 F 8 ) n C 4 F 8 C 4 F 8 C 4 F 8 0.8mTorr 103 cm RFID 3. FeCo-(C 4 F 8 ) n Intensity [a.u.] Magnetization [emu/cm 3 ] (1 1 0) M s H ce H ch Fe 70 Co 30 P C4F8 =0.8mTorr C 4 F 8 gas pressure [mtorr] 0.6mTorr 0.4mTorr 0mTorr (2 1 1) [deg.] Cu-K Fig. 3 X ray diffraction patterns for the FeCo-(C 4 F 8 ) n granular thin films prepared with the various partial pressure of fluorocarbon gas Coercivity [Oe] Fig. 4 Dependence of magnetization and coercivity on partial pressure of fluorocarbon gas for the FeCo-(C 4 F 8 ) n granular thin films. Resistivity [cm] C 4 F 8 gas pressure [mtorr] Fig. 5 Dependence of resistivity on partial pressure of fluorocarbon gas for the FeCo-(C 4 F 8 ) n granular thin films. 25

31 (1) FeCo FeCo (2) FeCo-(C 4 F 8 ) n FeCo (H ce ) 130 Oe 20 Oe (3) FeCo-(C 4 F 8 ) n 50 cm 4050 cm (4) FeCo-(C 4 F 8 ) n References 1) ; IC (2004). 2) S.Ohnumaetal.; J.Appl.Phys.,79(1996) ) S.Ohnumaetal.; J.Appl.Phys.,85(2000) ) KKakizakietAl.; JMagnMagnMater.310 (2007) e

32 Observation of plant tissues and cells by low temperature/low vacuum SEM Biology Section in the Faculty of Education Yasuko KANEKO Abstract Novel three dimensional images were obtained from rapidly frozen plant tissues and cells with a combination of the Alto 1000 cryo system and a low vacuum scanning electron microscope (Hitachi S-3400N). Segments of plant tissue were frozen in slush nitrogen and set in the cryo system. The sample was then fractured with a cooled knife and placed onto the specimen stage in the SEM. After appropriately subliming ice, a back scattered electron (BSE) image was obtained in low vacuum mode. While the fine structure of the cell surface could be observed with an accelerating voltage of 5 kv, intracellular ultrastructure was clearly visible through the cell wall at an accelerating voltage of 15 kv. The method allows the study of internal ultrastructure of plant cells and function close to the living state without lengthy specimen preparation process. 21 SEMHitachi S-3400NAlto 1000 (1) (2) (3) 30 Pa 1a 1b, c b 27

33 5kV䋬c 䈲ടㅦ㔚 15 kv 䈪 ኤ䈚䈢䉅䈱䈪䈅䉎䋮 1b 䈪䈲䋬 ᢿ䈮䉋䉍 䈛䈢 ᢿ䈚䈢 ო 䈱ᒻ 䈏䉋䈒䉒䈎䉎䋮 1c 䈪䈲䋬 䈱 䈮ᴪ䈦䈩ਗ䈹䋬 䈱䉋䈉䈭ᒻ䈱 䉕䋬 ო䉕ㅘㆊ䈚 䈩 ኤ䈜䉎䈖䈫䈏䈪䈐䈢䋮ᧄⵝ 䈪䈲䋬ᠲ ਛ䈮ടㅦ㔚 䉕ᄌ䈋䉎䈖䈫䈲 䉄䈩ኈᤃ䈪䋬 䇱䈫 䈭䉎ട ㅦ㔚 䉕ขᓧ䈜䉎䈖䈫䈏䈪䈐䉎䋮䉁䈢䋬㐳 㑆䈮䉒䈢䉎 ኤਛ䋬 ኤ ᢱ䈲䈾䈫䉖䈬ᄌൻ䈞䈝 ቯ䈚䈢 ᘒ䉕 䈦䈩䈇䈢䋮 a 100 um b c 10 um 10 um 1 ಓ ᢱ ኤ䉕 ᜰ䈚䈢ᣥ 䈱䉪䊤䉟䉥 SEM ⵝ 䈪䈲䋬 ᢱ 㕙䈮 䈜䉎㔮䉇䋬㔚ሶ ᾖ 䈱Ꮺ㔚䈏㓚ኂ䈫䈭䉍䋬㞲 䈭 䉕ᓧ䉎䈖䈫䈲 䉄䈩 㔍䈪䈅䈦䈢䋮ᧄⵝ 䈪䈲䋬 ᢱ䉴䊁䊷䉳䈱 ᣇ䈮䋬Ᏹ ᢱ䉴䊁䊷䉳䉋䉍ૐ䈇 ᐲ䉕 䈧䉝䊮䉼䉮䊮䉺䊚䊈䊷䉺䊷䈏 䈘䉏䈩䈍䉍䋬 ኤ ᢱ 㕙 䈮㔮䈏 䈜䉎䈖䈫䉕㒐䈇䈪䈇䉎䋮䉁䈢䋬ૐ 䊝䊷䊄䈪 ኤ䈜䉎䈖䈫䈮䉋䉍䋬 ᢱ 㕙䈏Ꮺ㔚䈜䉎䈖䈫䉅 䈭䈇䋮ടㅦ㔚 䉕ᄌ䈋䉎䈖䈫䈮䉋䉍䋬 ᢱ 㕙䈎䉌䈱 ᐲ䉕 ᤋ䈚䈢 䈒 䈭䉎 㔚ሶ 䋨 1b, c䋩䈏 ᓧ䉌䉏䉎䈖䈫䈲䋬ᣂ䈢䈭 䈪䈅䈦䈢䋮㐳 㑆䈮䉒䈢䉎㔚ሶ ᾖ 䈏น 䈪䈅䉎䈖䈫䈎䉌䋬㒝ዻ䈜䉎 EDX 䋨䉣䊈䊦䉩䊷ಽᢔ X ಽᨆⵝ 䋩䈪ర ಽᨆ䉕ⴕ䈉䈖䈫䉅䈪䈐䉎䋮 䈐䈩䈇䉎 ᘒ䈮ㄭ䈇 ㅧ䈫 䈱ዪ 䉕 ᜬ䈚䈩䈇䉎ᕆㅦಓ ᢱ䈱 ᓽ䉕ᵴ䈎䈚䈩䋬 䈱ᓸ ㅧ ኤ䈫ห 䈮䋬ర 䈱 ᚑ 䉇ಽᏓ䉕 ቯ䈜䉎䈖䈫䈮䉋䉍䋬ᯏ 䉕ត䉎䈖䈫䉅ᄞ䈪䈲䈭䈒䈭䈦䈢䋮 ᢥ₂㩷 1. Kaneko, Y., Matsushima, H., Wada, M., Yamada, M. A study of living plant specimens by low-temperature scanning electron microscopy. J. Electron Microsc. Tech. 2: 1-6 (1985) 2. Arai, M., Saito, T., Kaneko, Y., Matsushima, H. Observation of flower bud formation by a simple direct SEM viewing method. J. Electron Microsc. 45: (1996) 3. Nitta, K., Kaneko, Y. Simple plunge freezing applied to plant tissues for capturing the ultrastructure close to the living state. J. Electron Microsc. 53: (2004) 㪄㩷28㩷㪄

34 Solvent-induced chirality control in the enantioseparation via diastereomeric salt formation Department of Applied Chemistry Koichi KODAMA, Yuria KIMURA, Mikio YASUTAKE, Takuji HIROSE Abstract Solvent-induced chirality control in the enantioseparation of 1-phenylethylamine 1 by N-(p-toluenesulfonyl)-(S)-phenylalanine 2 via diastereomeric salt formation was studied. (S)-1 (S)-2 salt was preferentially crystallized as a less-soluble salt from aqueous alcohol, while (R)-1 (S)-2 salt was mainly obtained by addition of solvents with a six-membered ring such as 1,4-dioxane, cyclohexane, tetrahydropyran and cyclohexene to 2-propanol. Further investigations were carried out from the viewpoints of molecular structures and X-ray crystallographic analyses. Crystallographic analyses have revealed that incorporation of the six-membered ring solvent molecule in (R)-1 (S)-2 without hydrogen bonds changed the molecular conformation of (S)-2 to stabilize the salt, which changed the selectivity of 1 in the enantioseparation.. Fig. 1a a) b) Fig. 1 Schematic representations of the optical resolution methods via a) conventional diastereomeric salt formation and b) solvent switch method. 29

35 Fig. 1b 1. rac-1-phenylethylamine(1) N-(p-toluenesulfonyl)-L-phenylalanine(2) (S)-L-phenylalanine N-(p-toluenesulfonyl)-(S)-phenylalanine(2) (1) (S)-1 1,4- (R)-1 Table 1 Fig. 1b (S)-2 1 1,4- Table ,4-2- (S)-1 (R) Table 1. Optical resolution of racemic 1 with (S)-2 in water, alcohols and their mixture with 1,4-dioxane Table 2. Optical resolution of racemic 1 with (S)-2 in 2-PrOH/cyclic compounds mixed solvents. 30

36 2. (S)-2 N-(p-toluenesulfonyl)-(R)-phenylglycine (3) N-benzenesulfonyl-(S)-phenylalanine (4)2- rac-1 Table 3 1 (S)-2 Table 3. Optical resolution of racemic 1 with various resolving agents derived from amino acids. 3(R)-1 (S)-2,(S)-1 (S)-2,(R)-1 (S)-2 solvent 1 (R)-1 (S)-2 (R)-1 (S)-2 Fig. 2 1,4-6 (R)-1 (S)-2 (S)-1 (S)-2 (R)-1 (S)-2 solvent > (S)-1 (S)-2 >(R)-1 (S)-2 (S)-1 (S)-2 (R)-1 (S)-2 Figs (S)-2 (S)-2 (R)-1 (S)-2 solvent Fig. 2 4 (R)-1 (S)-2Fig. 3 3 (R)-1 (S)-2 solvent (R)-1 (S)-2 (S)-1 (S)-2Fig (S)-1 (S)-2(R)-1 (S)-2 solvent(r)-1 (S)-2 (R)-1 (S)-2 solvent > (S)-1 (S)-2 >(R)-1 (S)-2 31

37 Fig. 2 Crystal structure of (R)-1 (S)-2 cyclohexane. a) Packing of the hydrogen-bonded columns viewed down the columnar axis. b) A columnar structure consisting of four kinds of hydrogen bonds. Hydrogen atoms are omitted for clarity and cyclohexane molecules are shown with CPK model. The dotted lines and circles show the hydrogen bonds and columnar networks, respectively. Fig. 3 Crystal structure of (R)-1 (S)-2. a) Packing of the hydrogen-bonded columns viewed down the columnar axis. b) A columnar structure consisting of three kinds of hydrogen bonds Fig. 4 Crystal structure of (S)-1 (S)-2 viewed down the columnar axis. References 1) T. Hirose, M. Begum, M. S. Islam, K. Taniguchi, M. Yasutake, Tetrahedron Asymmetry, 2008, 19, ) K. Kodama, Y. Kimura, H. Shitara, M. Yasutake, R. Sakurai, T. Hirose, Chirality, in press. 32

38 GroEL Functional specialization of GroEL homologues in cyanobacteria Department of Biochemistry and Molecular Biology Hitoshi NAKAMOTO Abstract The photosynthetic prokaryotic cyanobacteria generally have two copies of the groel or chaperonin gene. The groel1 gene forms an operon with groes, whereas groel2 is not accompanied by groes. There is evidence for some specificity of in vivo function in these two GroELs. We have shown that GroEL1 can replace GroEL functionally in Escherichia coli, while GroEL2 cannot. GroEL1 appears to be essential in cyanobacteria, while the groel2 gene is dispensable under normal growth conditions. However, we showed that a groel2 mutant of Thermosynechococcus elongatus is high- and low-temperature sensitive. Our comparative biochemical characterization of the two GroELs showed that the cyanobacterial GroELs are mutually distinct and different from Escherichia coli GroEL. On the basis of our results, I propose the following hypothesis. GroEL1 plays an essential housekeeping role, like Escherichia coli GroEL. On the other hand, GroEL2 plays a role under stress that cannot be substituted by GroEL1. Cyanobacteria have acquired this unique chaperonin in order to sustain photoautotrophic life under changing environmental conditions. molecular chaperone 1 RNA Hsp proteostasis Hsp chaperonopathy HspsHspHsp60Hsp70Hsp90 Hsp100 Hsp 2 33

39 Hsp60 groel D86384GroEL groel GroEL Hsp60 groes 3 SDS-PAGE Hsp N GroEL GroEL groel 1993 GroEL DNA DNA DNA [ DNA ] 10 DNA 1 Hsp AB AB groel D78139 groes 4 groel groes groel1 groel2 GroEL 56 GroEL GroEL1 GroEL2 groel1 groel2 groel GroEL groel1 4 34

40 groel2 GroEL2 3 groel2 groel2 7 GroEL2 GroEL1 groel2 groel1 GroEL1 GroEL GroEL2 GroEL1 GroEL1GroEL2GroEL GroEL1GroEL2GroEL8 ATP GroEL 14 GroEL14 GroES GroEL 14 GroEL GroEL1 14 GroEL2 GroEL Ellis J. Proteins as molecular chaperones. Nature. 328: , CACS FORUM22: 20-26, Furuki, M., N. Tanaka, T. Hiyama and H. Nakamoto. Cloning, characterization, and functional analysis of groel-like gene from thermophilic cyanobacterium Synechococcus vulcanus, which does not form an operon with groes. Biochim. Biophys. Acta (Protein Structure and Molecular Enzymology), 1294: , Tanaka,N., T. Hiyama and H. Nakamoto. Cloning, characterization, and functional analysis of groesl operon from thermophilic cyanobacterium Synechococcus vulcanus. Biochim. Biophys. Acta (Protein Structure and Molecular Enzymology), 1343: , Nakamoto, H., M. Suzuki and K. Kojima. Targeted inactivation of the hrca repressor gene in cyanobacteria. FEBS Lett., 549: 57-62,

41 6. Kojima, K. and H. Nakamoto A novel light- and heat-responsive regulation of the groe transcription in the absence of HrcA or CIRCE in cyanobacteria. FEBS Lett., 581: , Sato, S., M. Ikeuchi, and H. Nakamoto. Expression and function of a groel paralog in the thermophilic cyanobacterium Thermosynechococcus elongatus under heat and cold stress. FEBS Lett., 582: , Huq, S., K. Sueoka, S. Narumi, F. Arisaka, and H. Nakamoto Comparative Biochemical Characterization of Two GroEL Homologs from the Cyanobacterium Synechococcus elongatus PCC 7942 Biosci. Biotechnol. Biochem., in press,

42 Research Supported by Analytical Instruments of Comprehensive Center for Science Department of Chemistry Toshio HASEGAWA Abstract I have carried out lots of research using various analytical instruments from Comprehensive Analysis Center for Science, Saitama University. Particularly the NMR spectrometers are a very useful tool to solve the following problems. (1) Structural analysis of novel aromatic compounds both in solution and solid state. (2) Detection of unstable reaction intermediates and monitoring the reaction process using a variable-temperature controlled system. (3) Elucidation of natural compounds using a high sensitivity device and many kinds of 2D NMR spectroscopic techniques (COSY, NOESY, HMBC, HSQC etc.) All of these studies would not have been possible to accomplish without the center , NMR NMR C NMR 1) 3. [2 + 2] 5 6 NMR NMR 100 NMR 37

43 7 NMR [2 + 2] [4 + 2] 2 2) 4. 1 mg 13 C NMR 2D NMR NMR 1 mg GC-MS NMR ) 5. (1) Machiguchi, T.; Hasegawa, T.; Kano, Y. Bull. Chem. Soc. Jpn. 1993, 66, (2) Machiguchi, T.; Hasegawa, T.; Ishiwata, A.; Terashima, S.; Yamabe, S.; Minato, T. J. Am. Chem. Soc. 1999, 121, (3) Hasegawa, T.; Toriyama, T.; Ohshima, N.; Tajima, Y.; Mimura, I.; Hirota, K.; Nagasaki, Y.; Yamada, H. Flavour and Fragrance J. 2010, in press. 38

44 Mechanism of photosynthetic activity-dependent transcriptional regulation elucidated by MALDI-TOF MS spectrometry anlysis using Autoflex III Department of Biochemistry and Molecular Biology Yukako HIHARA Abstract The redox state of the photosynthetic electron transport chain acts as a critical sensing mechanism by regulating the transcription of key genes involved in the acclimation response to a change in the environment. We have shown that small LuxR-type regulator, PedR, is involved in photosynthetic electron transport-dependent transcriptional regulation in the cyanobacterium Synechocystis sp. PCC We report here that thioredoxin (Trx) is identified as an interacting factor of PedR by pull-down assays and subsequent MALDI-TOF MS spectrometry analysis using Autoflex III. Under high-light conditions, it is likely that PedR is transiently inactivated upon reduction by reducing equivalents generated at the acceptor side of photosystem I and mediated by Trx. This is the first report showing the direct interaction between Trx and a transcriptional regulator to connect the redox state of the photosynthetic electron transport chain with changes in gene expression. Synechocystis sp. PCC 6803 S.6803 S.6803 S.6803 PedR (Photosynthetic electron transport dependent transcriptional regulator) (1)PedR PedR 39

45 PedR NHis PedR (His-PedR) S.6803 His-PedR His ()His-PedR His-PedR His-PedR SDS-PAGEHis-PedR 16 kda PedR 1 BRUKER Autoflex III m/z 2 fingerprint S.6803 Mascot http// S.6803 TrxMSlr0623 m/z = 1792) (MS/MS) LNTDENPNTASQYGIR TrxM 3 S

46 TrxM PedR PedR PedR TrxM PedR PedR 4 PedR PedR PedR PedR (2) (1) Nakamura K and Hihara Y (2006) Photon flux density-dependent gene expression in Synechocystis sp. PCC 6803 is regulated by a small, redox-responsive, LuxR-type regulator. Journal of Biological Chemistry 281: (2) Horiuchi M, Nakamura K, Kojima K, Nishiyama Y, Hatakeyama Y, Hisabori T and Hihara Y (2010) The PedR transcriptional regulator interacts with thioredoxin to connect photosynthesis with gene expression in cyanobacteria. Biochemical Journal 431:

47 SEC Purification of thiosialosides by a recycle-type SEC Division of Material Science Koji MATSUOKA Abstract An efficient separation between fully acetylated thiosialoside methyl esters and fully acetylated Neu5Ac2en methyl esters was accomplished by means of the SEC method. Purity and structural elucidation of the isolated compounds were performed by a combination of elemental analyses and spectroscopic analyses, including IR, 1 H, and 13 C NMR, and mass spectroscopic analyses. mm10-3 M 1970 Lee 1) 2) 3) 4) 5) (Size-exclusion chromatography; SEC) 6) 2,3-3 1 (KSAc) S N 2 2 1S N 2 HCl 2 3 TLC R f von Itzstein HPLC 5) SEC 7) 42

48 AcO AcHN OAc OAcCl OAc OAc COOMe O i) AcO COOMe AcHN O SAc OAc OAc OAc OAc O AcO AcHN OAc 3 1. Reagents and conditions: i) KSAc (5 molar excess), dichloromethane, 0 C rt, 2 d. COOMe H NMR 3A SEC 3 5 SEC SEC 2 (+ 3) + AcO AcO Br O O OAc 4 i) AcO AcHN OAc OAc COOMe O S OAc AcO AcO 5 O O OAc (+ 3) ii) 5 2 (+ 3) + AcO AcO Br O O OAc 6 iii) AcO AcHN OAc OAc COOMe AcO S O OAc AcO 7 O O OAc (+ 3) ii) 7 2. Reagents and conditions: i) Diethylamine (10 molar excess vs Br), DMF, 0 Crt, overnight; ii) purified by SEC; iii) K 2 CO 3, MeOH DMF, 0 C rt, 2 d, then Ac 2 O Pyr, rt, overnight. SEC (I)(impurity) I 4 II III 3 2 ( 3B) 5 ( 3D) 3 ( 3C) 1 H NMR SEC 7 43

49 OMe (A) CH= (aglycon) H-9b H-9a H-5 SCH 2 H-3eq (B) CH= (glycal) SAc (C) (D) 3. 1 H NMR spectra of (A) mixture of disaccharide 5 and glycal 3, (B) thioacetate 2, (C) glycal 3, and (D) pure disaccharide I II 80 Relative Intensity (RI response) Mixture load Impurity III II III 2nd cycle 3rd cycle Recycle 4th cycle Cut off Retention Time (hours) 4. SEC profile of the separation of disaccharide 5 and glycal 3. The inseparable mixture was injected into SEC columns at mixture load. 44

50 SEC 1 H NMR NMR 1) Y. C. Lee, R. R. Townsend, M. R. Hardy, J. Lönngren, J. Arnarp, M. Haraldsson, and H. Lönn, J. Biol. Chem., 258, 199 (1983). 2),, 111, 20 (1994). 3),, 39, 301 (2001). 4) a) K. Nishikawa, K. Matsuoka, E. Kita, N. Okabe, M. Mizuguchi, K. Hino, S. Miyazawa, C. Yamasaki, J. Aoki, S. Takashima, Y. Yamakawa, M. Nishijima, D. Terunuma, H. Kuzuhara, and Y. Natori, Proc. Natl. Acad. Sci. USA, 99, 7669 (2000); b) H. Oka, T. Onaga, T. Koyama, C.-T. Guo, Y. Suzuki, Y. Esumi, K. Hatano, D. Terunuma, and K. Matsuoka, Bioorg. Med. Chem. 17, 5465 (2009). 5) D.R. Groves,S.J. Bradley, F.J. Rose, M. Kiefel, and M. von Itzstein, Glycoconjugate J., 16, 13 (1999). 6) J.-I. Sakamoto, C. Takita, T. Koyama, K. Hatano, D. Terunuma, and K. Matsuoka, Carbohydr. Res. 343, 2735 (2008). 7) T. Kimura, F. Xue, T. Kobayashi, T. Onoda, and H. Yamamoto, Polymer J., 36, 205 (2004). 45

51 Atom Transfer Radical Polymerization of methyl methacrylate using iminopyrdineiron complexes immobilized into fluorotetrasilicic mica interlayer,,, Department of Applied Chemistry Takashi KONDO, Masa-aki OHSHIMA, Hideki KUROKAWA, Hiroshi MIURA Abstract The iminopyridine iron(iii) and (II) complexes were immobilized into fluorotetrasilicic mica interlayers through the intercalation of the iminopyridine ligand into the mica interlayers and simultaneous coordination of the ligand to the interlayer metal cations. The prepared catalysts were used for atom- transfer radical polymerization (ATRP) of methyl methacrylate (MMA). The Fe 3+ -based catalyst did not show a significant activity for the ATRP of MMA, whereas when ATRP was performed using the Fe 2+ -based catalyst, PMMA (poly(methyl methacrylate)) was obtained. Two peaks were observed in the GPC curve of the produced PMMA. Because polydispersity index was higher than 2, free-radical polymerization occurred simultaneously. To suppress the free-radical polymerization, we varied initiator/catalyst molar ratio. On increasing the molar ratio from 2/1 to 4/1 (favorable conditions for free-radical polymerization), PMMA with higher Mw was obtained. In contrast, by decreasing the molar ratio from 2/1 to 1/1 (favorable conditions for ATRP), PMMA with lower Mw was obtained. Those results clearly indicate that the lower Mw peak in the GPC curve corresponds to PMMA produced by ATRP R X Mt n Y R. X Mt n+1 Y Matyjaszewski 1) Sawamoto 2) Initiator Catalyst CH CH 2 C 3 Mt: central metal CO 2 CH X: halogen 3 Y: ligand (Atom Transfer Radical Polymerization : ATRP) CH CH 3 3 CH 2 C X Mt n. n+1 Y CH 2 C X Mt Y CO 2 CH CO 3 2 CH 3 Scheme 1 dormant species active species ATRP Scheme 1. Mechanism of ATRP 46

52 () ATRP 3),4) (MMA) ATRP Figure 1 MgO 6 SiO 4 SiO 4 tetrahedron Mg 2+ MgO 6 octahedron d 001 Na + Interlayer Na + cation Figure 1. Structure of fluorotetrasilicic mica () bis(imino)pyridine Fe 3+ 5) ATRP MMA ATRP ATRP Fe 2+ Fe 3+ N (Fe 2+ -mica, Fe 3+ -mica) 6) N iminopyridine ATRP 2,6-dimethyliminopyridine [PI(2,6-Me 2 )]Fe 3+ Fe 2+ Figure 2. 2,6-dimethyliminopyridine PMMA ligand 2. ME-100()() Fe/Na = 102 Fe 3+ -mica 200ºC, 4 h Fe 2+ -mica 200ºC, 4 h PI(2,6-Me 2 )70 ºC, 120 h ligand/mica = Fe 3+ :560 mol/g, Fe 2+ :850 mol/g 4 h (PI(2,6-Me 2 )/Fe 3+ -mica, PI(2,6-Me 2 )/Fe 2+ -mica) MMA ATRP 50 mol: 3.53 ml:mma 1.07 ml (10 mmol):ethyl 2-bromoisobutyrate (EBiB) 0.25 M 0.40 ml (0.10 mmol) 90ºC24 h 47

53 Na + N N Cation-exchange Fe 2+ or Fe 3+ Complex formation and immobilization into mica interlayer Figure 3. Outline of catalys preparation XRD Figure 4 Fe 3+, Fe nm 1.51 nm, 1.01 nm 1.51 nm 3-2. MMA ATRP MMA ATRP Table 1 PI(2,6-Me 2 )/Fe 3+ -micapmma PI(2,6-Me 2 )/Fe 2+ -mica PMMA Fe 2+ Fe 2+ Fe 3+ ATRP ATRP (Mw/Mn = 7.5)Fig 5(a) PMMA Intensity / arb unit 1.51 nm (d) 1.51 nm (b) 1.01 nm (c) 0.99 nm (a) / degree Figure 4. XRD profiles of (a) Fe 3+ -mica, (b) PI/Fe 3+ -mica, (c) Fe 2+ -mica, (d) PI/Fe 2+ -mica. Samples were analyzed after drying at 110 ºC for 1 h. The values in Figure 3 indicate the basal spacing (d 001 ) including the layer thickness. Table 1. Results for the polymerization of MMA using PI(2,6-Me 2 )/Fe n+ -mica catalysts (n=3 or 2) Catalyst T P *1 / ºC Time / h PMMA yield / g Conversion *2 / % Mn *3 / 10 4 Mw / Mn PI(2,6-Me 2 )/Fe 3+ -mica PI(2,6-Me 2 )/Fe 2+ -mica *1 T P = polymerization temperature. *2 Conversion = (PMMA yieldinitiator) / MMA. *3 Average-number molecular weight. solvent: toluene. molar ratio [M] 0 / [I] 0 / [catal] 0 =200 / 2 / 1. ATRP / Table 2 Figure 5 PMMA Figure 5 4/1 (b) 1/1 (c) PMMA ATRP PMMA 48

54 Table 2. Effect of the initiator/catalyst molar ratio Catalyst molar ratio [M] 0 / [I] 0 / [catal] 0 PMMA yield / g Conversion *1 / % Mn *2 / 10 4 Mw / Mn 200 / 4 / PI(2,6-Me 2 )/Fe 2+ -mica 200 / 2 / / 1 / Polymerization conditions: temperature 90 ºC, solvent toluene. *1 Conversion = (PMMA yieldinitiator) / MMA. *2 Average-number molecular weight. [I] 0 /[catal] 0 [I] 0 /[catal] 0 (b) 2 / 1 (a) 2 / 1 (c) 4 / 1 1 / Log M Log M Log M Figure 5. GPC curve of PMMA produced using PI/Fe 2+ -mica. molar ratio (a) [M] 0 /[I] 0 /[catal] 0 =200/2/1, (b) [M] 0 /[I] 0 /[catal] 0 =200/4/1, (c) [M] 0 /[I] 0 /[catal] 0 =200/1/1 4. PI(2,6-Me 2 )/Fe 3+ -mica PI(2,6-Me 2 )/Fe 2+ -mica ATRP Fe 3 PMMA Fe 2+ PMMA ATRP PMMA / ATRP PMMA PMMA References 1) K. Matyjaszewski, J. Xia, Chem. Rev. 2001, 101, ) M. Kamigaito, T. Ando, M. Sawamoto, Chem. Rev. 2001, 101, ) H. Bergenudda, M. Jonssona, D. Nystromb, E. Malmstrom, Journal of Molecular Catalysis, 2009, 306, 69. 4) S. Faucher, S. Zhu, Ind. Eng. Chem. Res. 2005,44, ) H. Kurokawa, M. Matsuda, K. Fujita, Y. Ishihama, T. Sakuragi, M. Ohshima, H. Miura, Chem Lett., 2007, 36, ) V. C. Gibson, R. K. O Reilly, D. F. Wass, A. J. P. White, D. J. Williams, Dalton Trans., 2003,

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64 (TBAUltramark) TBAUltramark 3. ESI/MS ppm Spec /5:43 (T /0.22:1.86) * =>MC[BP = 609.3, 5687] % Intensity m/z ISO:C54H59ClIrP2PtS % Intensity ESI/MS m/z HRMS() MS/MS 4. nanolc-esi/ms nanolc ESI/MS ECD(Electron Capture Dissociation) PEAKS ECD

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85 21 -Face-selective 1,3-dipolar cycloadditions of 3,4-di-tert-butylthiophene 1-oxide with 1,3-dipoles J. Nakayama, T. Furuya, Y. Suzuki, S. Hiraiwa, Y. Sugihara, Phosphorus, Sulfur Silicon Relat. Elem. 184, 1175 (2009). Synthesis and thermal decomposition of thiirane 1-imides of 2'-adamantylidene-9-benzonorbornenylidene Y. Sugihara, A. Kobiki, J. Nakayama, Heterocycles 78, 331 (2009). Synthesis and sulfuration of 2'-adamantylidene-9-benzonorbornenylidene Y. Sugihara, A. Kobiki, J. Nakayama, Heterocycles 78, 103 (2009). Effect of a metal salt on thiiranation of 2'-adamantylidene-9-benzonorbornenylidene with 4,4'-dithiodimorpholine and acetic anhydride Y. Sugihara, H. Koyama, J. Nakayama, Heterocycles 78, 325 (2009). Thiiranation of 2'-adamantylidene-9-benzonorbornenylidene using 4,4'-oligothiodimorpholine and Bronsted acid Y. Sugihara, H. Nozumi, J. Nakayama, Heteroat. Chem. 20, 12 (2009). Reactions of 9,9'-bibenzonorbornenylidene sulfoxides with TMSOTf: anomalous pinacol-type rearrangement of thiirane 1-oxides Y. Sugihara, S. Yamanaka, J. Nakayama, Heteroat. Chem. 20, 29 (2009). Preparation of some new bicyclic compounds of sulfur Y. Osawa, M. Aoki, O. Sato, T. Fujihara, J. Nakayama, J. Sulfur Chem. 30, 270 (2009). One-pot synthesis of bromo-tetracyanoazulenequinodimethanes and conducting properties of their charge transfer complexes with tetrathiotetracene O. Sato, M. Sato, H. Sugimoto, T. Kuramochi, T. Shirahata, K. Takahashi, J. Sulfur Chem. 30, 360 (2009). Reinvestigation on the synthesis of hexakis(phenylseleno)benzene M. Saito, Y. Kanatomi, J. Sulfur Chem. 30, 469 (2009). 80

86 Novel reactions of steric encumbered 1,4-dilithio-1,3-butadiene with group 14 electrophiles: formation and structure of stable dihydroxygermole M. Saito, M. Nakamura, T. Tajima, Heterocycles 78, 657 (2009). Synthesis and structure of the dithienostannole anion M. Saito, M. Shiratake, T. Tajima, J.-D. Guo, S. Nagase, J. Organomet. Chem. 694, 4056 (2009). Linkage isomerism of pentaammine(dimethylsulfoxide)ruthenium(ii/iii) complexes: A theoretical study M. Kato, T. Takayanagi, T. Fujihara, A. Nagasawa, Inorg. Chim. Acta 362, 1199 (2009). Group 12 metal complexes with inner-salt, bis(n,n-disubstituted amino)carbeniumdithiocarboxylate. Asymmetric stretching vibration of thiocarboxylate and reduction potential as probes for the coordination mode T. Sugaya, T. Fujihara, A. Nagasawa, K. Unoura, Inorg. Chim. Acta 362, 4813 (2009). Three syntheses of trans-cyclooctane-1,2-dithiol by ring opening of cis-cyclooctene episulfoxide with ammonium thiocyanate followed by reduction and reductions of trans-1,2-di(thiocyanato)cyclooctane and trans-1,2-cyclooctyl trithiocarbonate A. Ishii, A. Ono, N. Nakata, J. Sulfur Chem. 30, 236 (2009). Oxidation and reduction reactions of cis-9,10,11-trithiabicyclo[6.3.0]undecane synthesized by reaction of cis-cyclooctene with S8O A. Ishii, M. Suzuki, T. Sone, N. Nakata, Phosphorus, Sulfur Silicon Relat. Elem. 184, 1184 (2009). Zirconium Complex of an [OSSO]-Type Diphenolate Ligand Bearing trans-1,2-cyclooctanediylbis(thio) Core: Synthesis, Structure, and Isospecific 1-Hexene Polymerization A. Ishii, T. Toda, N. Nakata, T. Matsuo, J. Am. Chem. Soc. 131, (2009). Synthesis and Crystal Structures of the First Stable Mononuclear Dihydrogermyl(hydrido) Platinum(II) Complexes N. Nakata, S. Fukazawa, A. Ishii, Organometallics 28, 534 (2009). Reactions of 9-Triptyceneselenol with Palladium(0) Complexes: Unexpected Formations of the Dinuclear Palladium(I) Complex [{Pd(PPh 3 )} 2 (-SeTrip) 2 ] and Five-Membered Selenapalladacycle [Pd( 2 (C,Se)-Trip)(dppe)] N. Nakata, R. Uchiumi, T. Yoshino, T. Ikeda, H. Kamon, A. Ishii, Organometallics 28, 1981 (2009). Synthesis and X-ray structural analysis of hydrido(thiolato) platinum(ii) complexes N. Nakata, S. Yamamoto, W. Hashima, A. Ishii, Chem. Lett. 38, 400 (2009). 81

87 Path-integral molecular dynamics simulations of small hydrated sulfuric acid clusters H 2 SO 4 (H 2 O) n (n =1-6) on semiempirical PM6 potential surfaces A. Kakizaki, H. Motegi, T. Yoshikawa, T. Takayanagi, M. Shiga, M. Tachikawa, J. Mol. Struct. THEOCHEM 901, 1 (2009). Theoretical study on the transformation mechanism between dipole-bound and valence-bound anion states of small uracil-water clusters and their photoelectron spectra H. Motegi, T. Takayanagi, J. Mol. Struct. THEOCHEM 907, 85 (2009). Theoretical Study on the Mechanism of Low-Energy Dissociative Electron Attachment for Uracil T. Takayanagi, T. Asakura, H. Motegi, J. Phys. Chem. A 113, 4795 (2009). Path-integral molecular dynamics simulations of hydrated hydrogen chloride cluster HCl(H 2 O) 4 on a semiempirical potential energy surface T. Takayanagi, K. Takahashi, A. Kakizaki, M. Shiga, M. Tachikawa, Chem. Phys. 358, 196 (2009). Path-integral molecular dynamics simulations for water anion clusters (H 2 O) - 5 and (D 2 O) 5 T. Takayanagi, T. Yoshikawa, H. Motegi, M. Shiga, Chem. Phys. Lett. 482, 195 (2009). Path-integral molecular dynamics simulations of glycine (H 2 O) n (n=1-7) clusters on semi-empirical PM6 potential energy surfaces T. Yoshikawa, H. Motegi, A. Kakizaki, T. Takayanagi, M. Shiga, M. Tachikawa, Chem. Phys. 365, 60 (2009). Origin of the ambipolar operation of a pentacene field-effect transistor fabricated on a poly(vinyl alcohol)-coated Ta2O5 gate dielectric with Au source/drain electrodes S. Takebayashi, S. Abe, K. Saiki, K. Ueno, Appl. Phys. Lett. 94, /1 (2009). (2009) Vol. 15 No. 8 (2009) Kinetics of Photochromic Induced Energy Transfer between Manganese-Doped Zinc-Selenide Quantum Dots and Spiropyrans S. M. Emin, N. Sogoshi, S. Nakabayashi, T. Fujihara, C. D. Dushkin, J. Phys. Chem. C 113, 3998 (2009). Growth kinetics of CdS quantum dots and synthesis of their polymer nano-composites in CTAB reverse micelles S. Emin, N. Sogoshi, S. Nakabayashi, M. Villeneuve, C. Dushkin, J. Photochem. Photobiol., A 207, 173 (2009). 82

88 Induction of extracytoplasmic function sigma factors in Bacillus subtilis cells with membranes of reduced phosphatidylglycerol content M. Hashimoto, H. Takahashi, Y. Hara, H. Hara, K. Asai, Y. Sadaie, K. Matsumoto, Genes Genet. Syst. 84, 191 (2009). Rice BRITTLE CULM 5 (BRITTLE NODE) is involved in secondary cell wall formation in the sclerenchyma tissue of nodes T. Aohara, T. Kotake, Y. Kaneko, H. Takatsuji, Y. Tsumuraya, S. Kawasaki, Plant Cell Physiol. 50, 1886 (2009). Molecular cloning and expression in Pichia pastoris of a Irpex lacteus exo--(1 3)-galactanase gene T. Kotake, K. Kitazawa, R. Takata, K.Okabe, H. Ichinose, S. Kaneko, Y. Tsumuraya, Biosci., Biotechnol., Biochem. 73, 2303 (2009). Bifunctional cytosolic UDP-glucose 4-epimerases catalyse the interconversion between UDP-D-xylose and UDP-L-arabinose in plants T. Kotake, R. Takata, R. Verma, M. Takaba, D. Yamaguchi, T. Orita, S. Kaneko, K. Matsuoka, T. Koyama, W-D. Reiter, Y. Tsumuraya, Biochem. J. 424, 169 (2009). Isozyme-specific modes of activation of CTP:phosphorylcholine cytidylyltransferase in Arabidopsis thaliana at low temperature. R. Inatsugi, H. Kawai, Y. Yamaoka, Y. Yu, A. Sekiguchi, M. Nakamura, I. Nishida, Plant Cell Physiol. 50, 1717 (2009) Regulation of translation by the redox state of elongation factor G in the cyanobacterium Synechocystis sp. PCC 6803 K. Kojima, K. Motohashi, T. Morota, M. Oshita, T. Hisabori, H. Hayashi, Y. Nishiyama, J. Biol. Chem. 284, (2009). Physiological impact of thioredoxin- and glutaredoxin-mediated Redox regulation Cyanobacteria Y. Nishiyama, T. Hisabori, Adv. Bot. Res. 52, 187 (2009). Neuroendocrine regulation of thyroid-stimulating hormone secretion in amphibians R. Okada, T. Kobayashi, K. Yamamoto, T. Nakakura, S. Tanaka, H. Vaudry, S. Kikuyama, Ann. N. Y. Acad. Sci. 1163, 262 (2009). Impaired development of somatotropes, lactotropes and thyrotropes in growth-ratarted (grt) mice K. Kobayashi, K. Yamamoto, S. Kikuyama, T. Machida, T. Kobayashi, J. Toxicol. Pathol. 22, 187 (2009). 83

89 Demonstration of the proopiomelanocortin signaling system in the primary immune organ of the quail T. Kobayashi, A. Takaso, S. Tanaka, M. Amano, A. Takahashi, S. Iwamuro, T. Machida, Ann. N. Y. Acad. Sci. 1163, 441 (2009). Identification of ghrelin in the house musk shrew (Suncus murinus): cdna cloning, peptide purification and tissue distribution Y. Ishida, S. Sakahara, C.Tsutsui, H. Kaiya, I. Sakata, S. Oda, T. Sakai, Peptides (Amsterdam, Neth.) 30, 982 (2009). House musk shrew (Suncus murinus, order: Insectivora) as a new model animal for motilin study C. Tsutsui, K. Kajihara, T. Yanaka, I. Sakata, Z. Itoh, S. Oda, T. Sakai, Peptides (Amsterdam, Neth.) 30, 318 (2009). Cgr11 encodes a secretory protein involved in cell adhesion S. Devnath, T. Kataoka, K. Miura, M. Kusuda, K. Kitamura, Y. Kumada, A. Mochiduki, K. Kaneko, A. Adachi, K. Inoue, Eur. J. Cell Biol. 88, 521 (2009). Prolactin-Releasing Peptide regulates the cardiovascular system via corticotrophin-releasing hormone. T. Yamada, A. Mochiduki, Y. Sugimoto, Y. Suzuki, K. Itoi, K. Inoue, J. Neuroendocrinol. 21, 586 (2009). Blockage of PrRP attenuates MPTP-induced toxicity in mice. B. Sun, A. Mochiduki, K. Nakamura, K. Yokoyama, S. Adachi, K. Fujiwara, H. Matsumoto, K. Inoue, Peptides 30, 1267 (2009). Ultrasonic back reflection evaluation of crack growth from PSBs in low-cycle fatigue of stainless steel under constant load amplitude M. N. Islam, Y. Arai, Mater. Sci. Eng., A A520, 49 (2009). Ultrasonic wave intensity reflected from fretting fatigue cracks at bolt joints of aluminum alloy plates S. Wagle, H. Kato, NDT&E Int. 42, 690 (2009). A new development of chiral liquid crystals H. Nohira, Ekisho 13, 175 (2009). Development of chiral dopants for liquid crystal from chiral carboxylic acids H. Nohira, Y. Aoki, H. Shitara, T. Hirose, Fain Kemikaru 38, 43 (2009). 84

90 Catalytic enantioselective arylation of aryl aldehydes by chiral aminophenol ligands X.-F. Yang, T. Hirose, G.-Y. Zhang, Tetrahedron Asymmetry 20, 415 (2009). Bimetallic effect of silica-supported Pt-Ru catalyst for hydrogenation of aromatic hydrocarbons T. Arakawa, H. Seki, M. Ohshima, H. Kurokawa, H. Miura, Bull. Chem. Soc. Jpn. 82, 627 (2009). Support effect of palladium catalysts for naphthalene hydrogenation as model hydrogen storage process using low grade hydrogen containing CO K. Ezuka, M. Ohshima, H. Kurokawa, H. Miura, J. Jpn. Pet. Inst. 52, 10 (2009). Catalytic behavior of bis(imino)pyridineiron(ii) complex supported on clay minerals during slurry polymerization of ethylene Y. Hiyama, Y. Kawada, Y. Ishihama, T. Sakuragi, M. Ohshima, H. Kurokawa, H. Miura, Bull. Chem. Soc. Jpn. 82, 624 (2009). Dehydrogenation of propane combined with selective hydrogen combustion over Pt-Sn bimetallic catalysts S. Kaneko, T. Arakawa, M. Ohshima, H. Kurokawa, H. Miura, Appl. Catal., A 356, 80 (2009). Polymerization of ethylene using zirconocenes supported on swellable cation-exchanged fluorotetrasilicic mica H. Kurokawa, S. Morita, M. Matsuda, H. Suzuki, M. Ohshima, H. Miura, Appl. Catal., A 360, 192 (2009). Fabrication of zero-thermal-expansion ZrSiO4/Y2W3O12 sintered body I. Yanase, M. Miyagi, H. Kobayashi, J. Eur. Ceram. Soc. 29, 3129 (2009). A novel color former organogel for radiation detection systems H. Itoi, Y. Sekine, M. Sekiguchi, T. Tachikawa, Chem. Lett. 38, 1002 (2009). Synthesis of optically active spiro compounds with a 3,3'-(4H,4'H)-spirobi(2H-naphtho[1,2-b]pyran) skeleton and their applications as chiral dopants for nematic liquid crystals K. Tojo, T. Arisawa, Y. Aoki, D. Terunuma, Bull. Chem. Soc. Jpn. 82, 519 (2009). Wavelength conversion film with glass coated Eu chelate for enhanced silicon-photovoltaic cell performance T. Fukuda, S. Kato, E. Kin, K. Okaniwa, H. Morikawa, Z. Honda, N. Kamata, Opt. Mater. (Amsterdam, Neth.) 32, 22 (2009). 85

91 Specific heat-coefficient of YbAl3 studied by combined nearly free electron conduction band hybridized with localized f electrons with correlation effect, 67/1 (2009). Local area deposition of SiOC films by using a very-high-frequency atmospheric pressure microplasma jet from tetraethoxysilane Y. Ding, T. Kobayashi, H. Jia, H. Shirai, ECS Trans. 25, 1115 (2009). White light emission from silicon oxycarbide films prepared by using atmospheric pressure microplasma jet Y. Ding, H. Shirai, J. Appl. Phys. 105, /1 (2009). Crystallization process of amorphous silicon utilizing a radio-frequency thermal plasma torch N. Ohta, K. Haruta, H. Shimizu, T. Kobayashi, H. Shirai, ECS Trans. 25, 533 (2009). Crystallization of amorphous Si utilizing a RF thermal plasma torch at atmospheric pressure N. Ohta, K. Haruta, K. Shimizu, T. Kobayashi, H. Shirai, Purazuma Oyo Kagaku 17, 39 (2009). Crystallization of amorphous silicon utilizing the Rf plasma torch H. Shirai, Kagaku Kogyo 60, 128 (2009). Fluorescence quenching detection of peanut agglutinin based on photoluminescent silole-core carbosilane dendrimer peripherally functionalized with lactose K. Hatano, H. Saeki, H. Yokota, H. Aizawa, T. Koyama, K. Matsuoka, D. Terunuma, Tetrahedron Lett. 50, 5816 (2009). Synthesis and characterization of photo-responsive carbosilane dendrimers T. Koyama, K. Hatano, K. Matsuoka, Y. Esumi, D. Terunuma, Molecules 14, 2226 (2009). Synthetic construction of a Lex determinant via Gabriel amine synthesis and the glycopolymer involving highly clustered Lex residues K. Matsuoka, T. Kohzu, T. Hakumura, T. Koyama, K. Hatano, D. Terunuma, Tetrahedron Lett. 50, 2593 (2009). Syntheses and biological evaluations of carbosilane dendrimers uniformly functionalized with sialyl (23) lactose moieties as inhibitors for human influenza viruses H. Oka, T. Onaga, T. Koyama, C-T, Guo, Y. Suzuki, Y. Esumi, K. Hatano, D. Terunuma, K. Matsuoka, Bioorg. Med. Chem. 17, 5465 (2009). 86