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SCIENCE CHINA Chemistry

Contents Vol.55 No.10 October 2012

SPECIAL TOPIC: Physical Organic Chemistry in China Preface WU Yun-Dong, YU Zhi-Xiang & LIU Lei Sci China Chem, 2012, 55(10): 1989–1990

Special Topic·REVIEWS

Computational mechanistic studies of acceptorless dehydrogenation reactions catalyzed by transition metal complexes LI HaiXia & WANG ZhiXiang Sci China Chem, 2012, 55(10): 1991–2008

Ferric perchlorate-mediated radical reactions of [60]fullerene LI FaBao & WANG GuanWu Sci China Chem, 2012, 55(10): 2009–2017

NHX (X = F, Cl, Br, and I) hydrogen bonding in aromatic amide derivatives in crystal structures WANG DongYun, WANG JiLiang, ZHANG DanWei & LI ZhanTing Sci China Chem, 2012, 55(10): 2018–2026

Mechanistic aspects of oxidation of palladium with O2 JIN LiQun & LEI AiWen Sci China Chem, 2012, 55(10): 2027–2035

Theoretical studies and industrial applications of oxidative activation of inert C bond by metalloporphyrin-based biomimetic catalysis LIU Qiang & GUO CanCheng Sci China Chem, 2012, 55(10): 2036–2053

Special Topic·COMMUNICATIONS

Heterolytic and homolytic CD bond dissociation energies of NADH models in acetonitrile and primary isotopic effects on hydride versus hydrogen atom transfer reactions CAO ChaoTun, TAN Yue & ZHU Xiao-Qing Sci China Chem, 2012, 55(10): 2054–2056

Special Topic·ARTICLES

Mechanism of palladium-catalyzed decarboxylative cross- coupling between cyanoacetate salts and aryl halides JIANG YuanYe, FU Yao & LIU Lei Sci China Chem, 2012, 55(10): 2057–2062

Supramolecular vesicles of cationic gemini surfactants modulated by p-sulfonatocalix[4]arene LI ZhenQuan, HU ChunXiu, CHENG YuQiao, XU Hui, CAO XuLong, SONG XinWang, ZHANG HengYi & LIU Yu Sci China Chem, 2012, 55(10): 2063–2068

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Li+-templated complexation of cylindrical macrotricyclic host with naphthalene diimide: Cation-controlled switchable complexation processes ZENG Fei, SU YongSheng & CHEN ChuanFeng Sci China Chem, 2012, 55(10): 2069–2074

Theoretical study on formation of thioesters via O-to-S acyl transfer WANG Chen & GUO Qing-Xiang Sci China Chem, 2012, 55(10): 2075–2080

Car-Parinello molecular dynamics simulations of thionitroxide and S-nitrosothiol in the gas phase, methanol, and water —A theoretical study of S-nitrosylation LIANG Juan, CHENG ShangLi, HOU JunWei, XU ZhenHao & ZHAO Yi-Lei Sci China Chem, 2012, 55(10): 2081–2088

Azomethine ylide-formation from N-phthaloylglycine by photoinduced decarboxylation: A theoretical study FANG Qiu, DING LiNa & FANG WeiHai Sci China Chem, 2012, 55(10): 2089–2094

SCIENCE CHINA Chemistry

Contents Vol.55 No.10 October 2012

ARTICLES

Porous polymer supported palladium catalyst for cross coupling reactions with high activity and recyclability SUN Qi, ZHU LongFeng, SUN ZhenHua, MENG XiangJu & XIAO Feng-Shou Sci China Chem, 2012, 55(10): 2095–2103

Observation of the novel “three-pointed star” cage-like (H2O)5 cluster in a polymeric solid {[Ag2(bpp)2(H2O)2](chd)·9H2O}n LUO GengGeng, XIONG HongBo, FU ZhiYong & DAI JingCao Sci China Chem, 2012, 55(10): 2104–2114

Multi-component hydrogen-bonding salts formed between imidazole and aromatic acids: Synthons cooperation and crystal structures WANG Lei, ZHAO Lei, LIU Meng , CHEN RuiXin, YANG Yu & GU YuanXiang Sci China Chem, 2012, 55(10): 2115–2122

Nonlinear optical material of a low-dimensional coordination polymer: Synthesis, structure, NLO and fluorescence properties WANG Lei, ZHAO Lei, LIU Meng, CHEN RuiXin, YANG Yu & GU YuanXiang Sci China Chem, 2012, 55(10): 2123–2127

Sunlight responsive photocatalysts: AgBr/ZnO hybrid nanomaterial MENG ALan, QIU YanYan, ZHANG LiNa, XU Xiao & LI ZhenJiang Sci China Chem, 2012, 55(10): 2128–2133

Synthesis and biological activities of thio-triazole derivatives as novel potential antibacterial and antifungal agents WANG QingPeng, ZHANG JingQing, DAMU Guri L. V., WAN Kun, ZHANG HuiZhen & ZHOU ChengHe Sci China Chem, 2012, 55(10): 2134–2153

Amberlyst-15® in PEG: A novel catalytic system for the facile and efficient one-pot synthesis of benzothiazolo- [2,3-b]-quinazolinone derivatives MAZAAHIR Kidwai, RITIKA Chauhan & DIVYA Bhatnagar Sci China Chem, 2012, 55(10): 2154–2160

Crystal structures and thermal decomposition mechanism of four lanthanide complexes with halogen-benzoic acid and 1,10-phenanthroline WANG JuanFen, LI Hua, ZHANG JianJun, REN Ning & WU KeZhong Sci China Chem, 2012, 55(10): 2161–2175

Theoretical study of the charge carrier mobilities of the molecular materials tetrathiafulvalene (TTF) and 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP) LI HuiXue, WANG XiaoFeng, LI ZhiFeng, ZHENG RenHui & ZHU YuanCheng Sci China Chem, 2012, 55(10): 2176–2185

Quantum chemical study on excited states and charge transfer of oxazolo[4,5-b]-pyridine derivatives HE RongXing, YUAN YanJie, SHEN Wei, LI Ming & YAO Li Sci China Chem, 2012, 55(10): 2186–2196

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Mechanistic study and kinetic properties of the CF3CHO + Cl reaction GAO Hong, WANG Ying, WANG Qin & LIU JingYao Sci China Chem, 2012, 55(10): 2197–2201

High-selective removal of ultra-low level mercury ions from aqueous solution using oligothymonucleic acid functionalized polyethylene film YU Yang, ZHANG BoWu, YU Ming, DENG Bo, LI LinFan, FAN ChunHai & LI JingYe Sci China Chem, 2012, 55(10): 2202–2208

Toxicity of graphene oxide and multi-walled carbon nanotubes against human cells and zebrafish CHEN LiQiang, HU PingPing, ZHANG Li, HUANG SiZhou, LUO LingFei & HUANG ChengZhi Sci China Chem, 2012, 55(10): 2209–2216

The reductive mechanism of nitrobenzene catalyzed by nine charcoals in sulfides solution YU XiaoDong, GONG WenWen, LIU XinHui & BAO HuaYing Sci China Chem, 2012, 55(10): 2217–2223

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Variations of mercury distribution in the water column during the course of a tidal cycle in the Yangtze Estuarine intertidal zone, China Bi ChunJuan, CHEN ZhenLou, SHEN Jun & SUN WeiWei Sci China Chem, 2012, 55(10): 2224–2232

Estimating emissions of HCFC-22 and CFC-11 in China by atmospheric observations and inverse modeling AN XingQin, HENNE Stephan, YAO Bo, VOLLMER Martin K., ZHOU LingXi & LI Yan Sci China Chem, 2012, 55(10): 2233–2241

NEWS & COMMENTS

International Year of Crystallography, 2014 DESIRAJU Gautam R. Sci China Chem, 2012, 55(10): 2242–2243

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• COMMUNICATIONS • October 2012 Vol.55 No.10: 2054–2056 · SPECIAL TOPIC · Physical Organic Chemistry in China doi: 10.1007/s11426-012-4679-6

Heterolytic and homolytic CD bond dissociation energies of NADH models in acetonitrile and primary isotopic effects on hydride versus hydrogen atom transfer reactions

CAO ChaoTun, TAN Yue & ZHU Xiao-Qing*

State Key Laboratory of Elemento-Organic Chemistry; Department of Chemistry, Nankai University, Tianjin 300071, China

Received March 28, 2012; accepted May 21, 2012; published online July 15, 2012

Heterolytic and homolytic CD bond dissociation energies of three NADH models: BNAH-4,4-d2, HEH-4,4-d2 and AcrD2 in acetonitrile were first estimated by using an efficient method. The results showed that the heterolytic CD bond dissociation energies are 65.2, 70.2, and 81.9 kcal/mol and the homolytic CD bond dissociation energies are 72.66, 70.69, and 74.95 kcal/mol for BNAH-4,4-d2, HEH-4,4-d2, and AcrD2, respectively. According to the bond dissociation energy differences of isotope isomers, an interesting conclusion can be made that the primary kinetic isotope effects are dependent not only on the zero-point energy difference of the isotope isomers, but also on the types of CD bond dissociations, and the CD bond homolytic dissociations should have much larger primary kinetic isotope effects (26.928.8) than the corresponding CD bond heterolytic dissociations (3.9–5.4).

bond dissociation energies, primary isotopic effects, nicotinamide-adenine dinucleotide coenzyme models

Isotope effects can be extremely informative in mechanistic effect deals directly with the dissociations of chemical studies of organic and bioorganic reactions, especially for bonds containing isotopic-atoms, the dissociation energies the reactions involving hydrogen (including hydride and of the bonds containing isotopic atom would be more relia- proton) transfer [1]. According to the theory of isotope ble and reasonable thermodynamic data than the corre- effects described in current many textbooks and literatures sponding zero-point energy of the isotopic isomer to esti- [2], the origin of the primary isotope effect is only due to mate the primary isotope effect. Systematic examination of the difference of zero-point energies between the related the past publications on this subject shows that although isotopic isomers, that is, the primary isotope effects are only much attention has been paid to dissociation energy deter- caused by the state energy difference of the two isotopic mination of chemical bonds containing general hydrogen isomers as reactants, but are utterly foreign to the state en- atom [3], there are no efficient methods to directly deter- ergies of the bond dissociation products of the isotopic mine the dissociation energies of the chemical bonds con- molecules and the dissociation types of the bonds contain- taining the corresponding isotope atom (such as D atom) in ing isotopic atoms (e.g. heterolysis and homolysis). It is solution until now. Herein we wish to report an efficient and evident that such understanding about the origin of primary luck-given experimental method, which can be used to esti- isotope effect should be extremely ex parte, which certainly mate the heterolytic and homolytic CD bond dissociation brings many unreliable even incorrect evaluations on the energies of the three important models of nicotinamide- primary isotope effects. Since the primary kinetic isotope adenine dinucleotide coenzyme (NADH): BNAH-4,4-d2 [4a], HEH-4,4-d2 [4b] and AcrD2 [4c] (Scheme 1) in acetonitrile. *Corresponding author (email: [email protected]) In a previous contribution [5], we reported the determi-

Table 1 Enthalpy changes of Eqs. (1) and (2), enthalpy changes of deprotonation of TMPAH+ and dedeuteration of TMPAD+, heterolytic CH and CD bond dissociation energies (kcal/mol) together with the maximum kinetic isotopic effects

a) a) b) c) d) NADH Hr(1) Hr(2) Hhet(CH) Hhet(CD) kH/kD BNAH 38.0 38.0 64.2 65.2 5.4 Scheme 1 Structures of the three deuterated NADH models and N,N, HEH 69.3 70.2 4.7 N′,N′-tetramethyl-p-phenylene-diamine radical cation. 32.9 33.0

AcrH2 21.1 21.3 81.1 81.9 3.9 + e) + e) HP(TMPAH ) = 9.1 HP(TMPAD ) = 10.1 nation of heterolytic and homolytic CH bond dissociation a) Hr obtained from the reaction heat of Eqs. (1) and (2) by switching energies of the three NADH models in acetonitrile accord- the sign of the heat values, the latter was measured by titration calorimetry ing to the reaction of the NADH models with N,N,N′,N′- in acetonitrile at 25 °C under an atmosphere of argon. The data given in kcal/mol were average values of at least three independent runs, each of tetramethyl-p-phenylene-diamine radical cation perchlorate which was again an average value of eight consecutive titrations, except the +•  (TMPA ClO4 ) Eq. (1). According to Eq. (1), when the first. Uncertainty is smaller than 0.3 kcal/mol. b) From ref. [5(a)]. c) Calcu- deuterated NADH models were used to replace the corre- lated according to Eq. (4). d) Calculated according to the equation: kH/kD = exp(H/RT) [6], where H = Hhet(CD)  Hhet(CH). e) Obtained sponding non-deuterated NADH models to react with +  +  +•  from the corresponding reaction heats of TMPA with H ClO4 or D ClO4 in TMPA ClO4 , Eq. (2) can be obtained. But unlike the cor- acetonitrile, the latter was measured by titration calorimetry at 298 K under responding C-H bond dissociation energies, the CD bond an atmosphere of argon. Uncertainty is smaller than 0.3 kcal/mol. dissociation energies of the NADH models can not be determined by Eq. (2), because the values of E0(D+/0) and work; [Hf(NADH)–Hf(NADH-4-d)] is the difference of 0 0/ E (D ) are unavailable till now. However, if Eq (1) was formation enthalpies between BNAH and BNAH-4-d, reduced by Eq. (2), Eq. (3) can be obtained. From Eq. (3), which is equal to the difference of the zero-point energies we are surprise to find that the heterolytic CD bond disso- between NADH and NADH-4-d (ZPE), and the latter can ciation energies of the NADH models can be derived, since be derived from the difference of stretching vibration be- Eq. (4) can be easily deduced from Eq. (3). In Eq. (4), tween the CH bond and the CD bond according to ZPE Hhet(CH) is heterolytic CH bond dissociation energies   = 1/2hcL(vCH – vCD) [6]. [Hf(D )Hf(H )] is the differ- of the NADH models, which are available from our previ- ence of formation enthalpies between H atom and D atom, it + ous work; [5] Hr(1) and Hr(2) as well as HP(TMPAD ) can be obtained from the BDE’s of HH and DD [7], since and H (TMPAH+) are the enthalpy changes of the Eqs. (1) P the standard formation enthalpies of H2 (g) and D2 (g) all and (2), as well as the enthalpy changes of the deprotona- are equal to zero at 25 °C [8]. The detailed experimental + + tion of TMPAH and the dedeuteration of TMPAD , the results are summarized in Table 2. values of them all can be obtained from the corresponding NADH  NAD• + H• (5) reaction heats, which can be directly determined by using NADH-4-d  NAD• + D• (6) titration calorimetry. The detailed experimental results are (5) – (6): summarized in Table 1. • • NADH + D  NADH-4-d + H (7) NADH + 2TMPA+•  NAD+ + TMPA + TMPAH+ (1) Hhomo(C–D) = Hhomo(C–H) + [Hf(NADH)– +• + • • NADH-4,4-d2 + 2TMPA  NAD-4-d + TMPA + Hf(NADH-4-d] + [Hf(D ) – Hf(H )] (8) + TMPAD (2) From Table 1, it is clear that the heterolytic CD bond (1) – (2): dissociation energies of the three NADH models are 65.2, + + NADH + NADH-4-d + TMPAD  NADH-4,4-d2 + 70.2 and 81.9 kcal/mol for BNAH-4,4-d2, HEH-4,4-d2 and NAD+ + TMPAH+ (3) AcrD2, respectively, which are larger than the correspond- + ing C-H bond heterolytic dissociation energies by 1.0, 0.9 Hhet(CD) = Hhet(CH) + [Hp(TMPAD ) – + and 0.8 kcal/mol, respectively. From Table 2, it is found HP(TMPAH )] – [Hr(1) – Hr(2)] (4) that the homolytic CD bond dissociation energies of the Using a similar experimental strategy used to obtain the three NADH models are 72.7, 70.7 and 75.0 kcal/mol for heterolytic CD bond dissociation energies of the NADH BNAH-4,4-d2, HEH-4,4-d2 and AcrD2, respectively, which models, the homolytic CD bond dissociation energies of are larger than the corresponding C-H bond homolytic dis- the NADH models in acetonitrile can be obtained from Eq. sociation energies by 2.0, 2.0 and 2.0 kcal/mol, respectively. (8), which was formed according to Eq. (7), and the latter Comparison of the three differences of the CH bond and was just derived from the difference of the two defined Eqs. the CD bond dissociation energies clearly shows that the (5) and (6) of the corresponding CH and CD bonds ho- difference of the CH bond and the CD bond homolytic molytic dissociation energies. In Eq. (8), Hhomo(CH) is dissociation energies is larger than the difference of the the homolytic CH bond dissociation energies of the corresponding CH bond and the CD bond heterolytic NADH models, which can be obtained from our previous dissociation energies by ca. 1 kcal/mol for the three NADH 2056 Cao CT, et al. Sci China Chem October (2012) Vol.55 No.10

Table 2 Stretching vibration frequencies of the CH and CD bonds estimated by using experimental method, which, to our 1 (cm ), homolytic dissociation energies of the CH, CD, HH and DD knowledge is first reported. This result indicates that from bonds (kcal/mol) together with the maximum kinetic isotopic effects the CD bond dissociation energies of view, kinetic isotope a) a) b) c) d) NADH v(CH) v(CD) Hhomo(CH) Hhomo(CD) kH/kD effect is not only dependent on the zero-point energy dif- BNAH 2820.0 2079.4 70.7 72.7 29.2 ference of the isotope isomers but also dependent on the HEH 2864.9 2100.4 68.7 70.7 29.2 types of CD bond dissociations, which evidently has great

AcrH2 2808.9 2075.1 73.0 75.0 29.2 interesting to further understand the source and essence of e) e) Ghomo(HH) = 104.15 kcal/mol Ghomo(DD) = 105.96 kcal/mol kinetic isotope effect. a) Vibration frequencies were derived from IR measurement (see Sup- porting Information). Uncertainty is smaller than 10 cm1. b) Derived from the literature results [5(a)] after revision according to the re-measured Financial support from the National Natural Science Foundation of China redox potentials of the NADH models and their salts in acetonitrile by (21072104, 20921120403 and 20832004), the National Basic Research using Osteryoung square wave voltammetry (OSWV), since OSWV has Program of China (2004CB719905) and the 111 Project (B06005) is been verified to be more accurate method to estimate the standard gratefully acknowledged. one-electron redox potentials of analyte with irreversible electrochemical processes [9]. c) Calculated according to Eq. (8). d) Calculated according to the equation: kH/kD = exp(H/RT) [6], where H = Hhomo(CD) - 1 (a) Melander L. Isotope Effects on Reaction Rates. New York: Hhomo(CH). e) From ref. [7]. Ronald Press. 1960; (b) Melander L, Saunders WH Jr. Reaction Rates of Isotopic Molecules. 2nd ed. New York: Wiley. 1980; (c) Almars- models, which indicates that the difference of the CH bond son O, Sinha A, Gopinath E, Bruice TC. Mechanism of one-electron oxidation of NAD(P)H and function of NADPH bound to catalase. J and the CD bond dissociation energies is not only de- Am Chem Soc, 1993, 115: 7093–7102 pendent on the zero-point energy difference of the isotopic 2 (a) Isaacs NS. Physical Organic Chemistry. 2nd ed. New York: John isomers, but also dependent on the formation enthalpy dif- Wiley & Sons. 1995. 287 318; (b) Page M, Williams A. Organic ference of the corresponding products of the bond dissocia- and Bio-organic Mechanism. England: Addison Wesley Longman. 1997. 80–96; (c) Wiberg KB. The deuterium isotope effect. Chem tions. According to the difference of the CH bond and the Rev, 1955, 55: 713 CD bond heterolytic bond energies of the three NADH 3 (a) Ellis WW, Raebiger JW, Curtis CJ, Bruno JW, DuBois DL. Hy- models, the maximum kinetic isotope effects can be esti- dricities of BzNADH, C5H5Mo(PMe3)(CO)2H, and C5Me5Mo(PMe3)- (CO)2H in acetonitrile. J Am Chem Soc, 2004, 126: 2738–2743; (b) mated, the results are 5.4, 4.7, and 3.9 for BNAH-4,4-d2, Handoo KL, Cheng J-P, Parker VD. Hydride affinities of organic HEH-4,4-d2 and AcrD2, respectively. Evidently, such esti- radicals in solution. A comparison of free radicals and carbenium mations are close to or smaller than the results (5.96, 6.31 ions as hydride ion acceptors. J Am Chem Soc, 1993, 115: 5067–5072 and 5.81 for BNAH, HEH and AcrH , respectively) estimat- 4 (a) Fukuzumi S, Tokuda JY, Etano T, Okamoto T, Otera J. Electron- 2 transfer oxidation of 9-substituted 10-methyl-9,10-dihydroacri- dines ed only from the corresponding zero-point energy difference cleavage of the carbon-hydrogen vs carbon-carbon bond of the radi- of the two isotopic isomers. But, according to the difference cal cations. J Am Chem Soc, 1993, 115: 8960–8968; (b) Ouellet SG, of the CH bond and the CD bond homolytic dissociation Tuttle JB, MacMillan DWC. Enantioselective organocatalytic hy- energies, the maximum kinetic isotope effects can be dride reduction. J Am Chem Soc, 2005, 127: 32–33; (c) Yuasa J, Yamada S, Fukuzumi SA. Mechanistic dichotomy in scandium estimated to be 29.2 for BNAH-4,4-d2, HEH-4,4-d2 and ion-promoted hydride transfer of an NADH analogue: Delicate bal- AcrD2, which are quite larger than the value only derived ance between one-step hydride-transfer and electron-transfer path- from the zero-point energy difference of the two isotopic ways. J Am Chem Soc, 2006, 128(46): 14938–14948 isomers [10]. These results clearly indicate that when the 5 (a) Zhu X-Q, Li H-R, Li Q, Ai T, Lu J-Y, Yang Y, Cheng J-P. De- termination of the C4−H bond dissociation energies of NADH models origin of kinetic isotope effects was due to the difference of and their radical cations in acetonitrile. Chem Eur J, 2003, 9: the CD bond and the CH bond dissociation energies, the 871–880; (b) Zhu X.-Q, Yang Y, Zhang M, Cheng J-P. First estima- kinetic isotope effects on the reactions of the NADH models tion of C4−H bond dissociation energies of NADH and its radical are not only dependent on the zero-point energies of the iso- cation in aqueous solution. J Am Chem Soc, 2003, 125: 15298–15299 6 Neil S. Physical Organic Chemistry. 2nd ed. Longman Press: topic isomers, but also dependent on the types of CD bond London, 1995. 293 dissociations. If the hydride transfer from the NADH models 7 Luo YR. Handbook of Bond Dissociation Energies in Organic Com- takes place by the CH bond heterolytic dissociation, the pounds. CRC press, 2002 8 Levine I. Physical Chemistry. 2nd ed. New York: McGraw-Hill Inc. maximum kinetic isotope effects range from 3.9 to 5.4, but if 1983. 868 the hydrogen transfer from the NADH models takes place 9 Zhu X-Q, Zhang M-T, Yu O, Wang C-H, Cheng J-P. Hydride, hy- by the CH bond homolytic dissociation, the maximum ki- drogen atom, proton, and electron transfer driving forces of various netic isotope effects are 29.2, that is, neutral hydrogen atom five-membered heterocyclic organic hydrides and their reaction in- termediates in acetonitrile. J Am Chem Soc, 2008, 130: 2501–2516 transfer generally has much larger kinetic isotope effect than 10 It is worthy to mention herein that in some cases, kinetic isotopic ef- hydride anion transfer, which, in fact, has been supported by fect were reported to be larger than the estimated values, which can a mass of experimental observations [11]. be due to the tunneling effects. In conclusion, the CD bond heterolytic and homolytic 11 (a) Nagel ZD, Klinman JP. Tunneling and dynamics in enzymatic hydride transfer. Chem Rew, 2006, 106: 3095–3118; (b) Klinman JP. dissociation energies of the three typical NADH models: Dynamic barriers and tunneling new views of hydrogen transfer in BNAH-4,4-d2, HEH-4,4-d2 and AcrD2 in acetonitrile were enzyme reactions. Pure Appl Chem, 2003, 75(5): 601–608

SCIENCE CHINA Chemistry Vol. 55 No. 10 October 1 2012 (Monthly)

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