Sample records for diprotons

  1. The Effect of Hypothetical Diproton Stability on the Universe

    R. A. W. Bradford


    By calculation of the proton–proton capture cross-section, it is shown that the existence of a bound diproton state would not lead to significant production of diprotons during big bang nucleosynthesis, contrary to popular belief. In typical stellar interiors, the stability of diprotons would lead to a reaction pathway for converting protons to deuterons perhaps ∼ 1010 times faster than the usual weak capture reaction. This would prevent stars of the familiar hot, dense type from occurring in the universe. However, if diproton stability is achieved by an increase in the low-energy strong coupling, , then stars with temperatures and densities sufficiently reduced so as to offset the faster reaction pathway to deuterium will appear to meet elementary stability criteria. The claim that there is a fine-tuned, anthropic upper bound to the strong force which ensures diproton instability therefore appears to be unfounded.

  2. Manifestation of the $P$-wave diproton resonance in single-pion production in $pp$ collisions

    Platonova, M N


    It is demonstrated that many important features of single-pion production in $pp$ collisions at intermediate energies ($T_p \\simeq 400$-$800$ MeV) can naturally be explained by supposing excitation of intermediate diproton resonances in $pp$ channels ${}^1D_2$, ${}^3F_3$ and ${}^3P_2$, in addition to conventional mechanisms involving an intermediate $\\Delta$-isobar. We predict for the first time the crucial role of the ${}^3P_2$ diproton resonance, found in recent experiments on the single-pion production reaction $pp \\to pp({}^1S_0) \\pi^0$, in reproducing the proper behavior of spin-correlation parameters in the reaction $pp \\to d \\pi^+$ which were poorly described by conventional meson-exchange models to date. The possible quark structure of the $P$-wave diproton resonances is also discussed.

  3. Unusual cis-diprotonated forms and fluorescent aggregates of non-peripherally alkoxy-substituted metallophthalocyanines.

    Kasprzycki, P; Sobotta, L; Lijewski, S; Wierzchowski, M; Goslinski, T; Mielcarek, J; Radzewicz, C; Fita, P


    Protonation and aggregation of two metallophthalocyanines (zinc and magnesium) non-peripherally substituted with 1,4,7-trioxanonyl moieties were studied by steady-state and time-resolved optical spectroscopy. Both compounds are easily protonated in organic solvents, but the central metal ion strongly affects the character of this process. In particular, the magnesium derivative forms the cis-diprotonated isomer observed for the first time in phthalocyanines, in contrast to its zinc counterpart which forms the typical trans-diprotonated isomer. In addition, studies performed on phthalocyanines substituted with n-butoxy groups at their non-peripheral positions indicated that the formation of the cis-diprotonated forms is a more common feature of alkoxy-substituted magnesium metallophthalocyanines, in contrast to derivatives with other metal ions. The cis-diprotonated forms of the magnesium derivatives are formed at much lower proton concentrations than the trans-diprotonated forms of their zinc counterparts. The cis-isomers were also found to have more advantageous photophysical properties for photoactive applications than the trans-isomers. Aggregation studies of the trioxanonyl phthalocyanines revealed that the magnesium derivative aggregates much more easily in non-coordinating solvents than its zinc counterpart. Both the derivatives form fluorescent aggregates, which is typically attributed to the presence of oxygen-to-metal intermolecular coordination preventing the formation of non-fluorescent face-to-face stacks. The results indicate that the oxygen-to-metal coordination plays a significant role in the studied systems and the stronger oxygen-coordination ability of magnesium ions compared to zinc ions may underlie the observed differences between the phthalocyanines metallated with these two ions.

  4. Binding the Diproton in Stars: Anthropic Limits on the Strength of Gravity

    Barnes, Luke A


    We calculate the properties and investigate the stability of stars that burn via strong (and electromagnetic) interactions, and compare their properties with those that, as in our Universe, include a rate-limiting weak interaction. It has been suggested that, if the diproton were bound, stars would burn ~10^{18} times brighter and faster via strong interactions, resulting in a universe that would fail to support life. By considering the representative case of a star in our Universe with initially equal numbers of protons and deuterons, we find that stable, "strong-burning" stars adjust their central densities and temperatures to have familiar surface temperatures, luminosities and lifetimes. There is no "diproton disaster". In addition, strong-burning stars are stable in a much larger region of the parameter space of fundamental constants, specifically the strength of electromagnetism and gravity. The strongest anthropic bound on stars in such universes is not their stability, as is the case for stars limited...

  5. Measurements on diproton emission from the break-up channels of 23Al and 22Mg



    Two-proton relative momentum distributions from the break-up channels 23Al→p+p+21Na and 22Mg→p+p+20Ne at an energy of 60-70 A MeV have been measured together with two-proton opening angles at the projectile fragment separator beamline (RIPS) in the RIKEN Ring Cyclotron Facility. The results demonstrate the existence of diproton emission component from single-step 2He for highly excited 23Al and 22Mg.

  6. Di-proton decay of the 6.15 MeV 1- state in 18Ne

    Brown, B. A.; Barker, F. C.; Millener, D. J.


    The widths for one- and two-proton decay of the 1-2 state in 18Ne are calculated. Shell-model wave functions are used to obtain the spectroscopic factors. The R-matrix theory of Barker which incorporates the final-state interaction between the two protons is used for the di-proton decay model. The calculated widths for both one- and two-proton decay are in qualitative agreement with experiment. We find that the decay width for sequential two-proton decay through the ghost of the 1/2+ bound state in 17F is comparable to the width of the direct di-proton decay.

  7. Contribution of pH, diprotonated phosphate and potassium for the reflex increase in blood pressure during handgrip

    Boushel, Robert Christopher; Madsen, P; Nielsen, H B


    The relative importance of pH, diprotonated phosphate (H2PO4-) and potassium (K+) for the reflex increase in mean arterial pressure (MAP) during exercise was evaluated in seven subjects during rhythmic handgrip at 15 and 30% maximal voluntary contraction (MVC), followed by post-exercise muscle...... ischaemia (PEMI). During 15% MVC, MAP rose from 92 +/- 1 to 103 +/- 2 mmHg, [K+] from 4.1 +/- 0.1 to 5.1 +/- 0.1 mmol L-1, while the intracellular (7.00 +/- 0.01 to 6.80 +/- 0.06) and venous pH fell (7.39 +/- 0.01 to 7.30 +/- 0.01) (P increased 8.4 +/- 2 mmol kg-1...

  8. Synthesis and Crystal Structure of the Perchlorate Salt of Diprotonated 2,3-Di-2-pyridyl-5-nitroquinoxaline


    The diprotonated perchlorate salt of 2,3-di-2-pyridyl-5-nitroquinoxaline [C18H13N5O2](ClO4)2((CH3OH)((C2H5OH) has been synthesized and characterized by elemental analysis, IR and NMR spectra. X-ray diffraction analysis at room temperature indicates that the title compound (C21H23N5O12Cl2, Mr = 608.34) crystallizes in triclinic, space group P ī with a = 7.992(8), b = 12.82(1), c = 13.42(1) (A), α= 104.77(2), β = 97.84(2), γ = 95.48(2), V = 1305(2) (A)3, Z = 2, Dc = 1.549 g/cm3, F(000) = 628 and ((MoK() = 0.317 mm-1. The final R and wR factors are 0.0566 and 0.1016, respectively with 4325 independent reflections. The quinoxaline ring makes the dihedral angles of 44.2(2) and 33.9(5)( with two protonated pyridine rings whose dihedral angle is 48.1(6)(. The favored orientation of two protonated pyridine rings is that their N atoms are opposite to each other. There exist intra- and inter-molecular N-H…O hydrogen bonds and π…π interactions which stabilize the structure further.

  9. Diprotonation process of meso-tetraphenylporphyrin derivatives designed for Photodynamic Therapy of cancers: From Multivariate Curve Resolution to predictive QSPR modeling

    Chauvin, Benoit, E-mail: [Univ. Paris-Sud, EA 4041, IFR 141, Faculte de Pharmacie, F-92296 Chatenay-Malabry (France); Institut Curie, UMR 176 CNRS, Centre Universitaire, Univ Paris-Sud, F-91405 Orsay (France); Kasselouri, Athena; Chaminade, Pierre; Quiameso, Rita [Univ. Paris-Sud, EA 4041, IFR 141, Faculte de Pharmacie, F-92296 Chatenay-Malabry (France); Nicolis, Ioannis [Laboratoire de Biomathematiques et Informatique, Departement de Sante publique et biostatistiques et EA 4466, Faculte de Pharmacie, Universite Paris Descartes, 4, avenue de l' Observatoire, 75270 Paris cedex 06 (France); Maillard, Philippe [Institut Curie, UMR 176 CNRS, Centre Universitaire, Univ Paris-Sud, F-91405 Orsay (France); Prognon, Patrice [Univ. Paris-Sud, EA 4041, IFR 141, Faculte de Pharmacie, F-92296 Chatenay-Malabry (France)


    Highlights: {yields} Diprotonation of 17 meso-tetraphenylporphyrin derivatives. {yields} MCR-ALS resolution of multi-component mixtures. {yields} Determination of stepwise protonation constants. {yields} Prediction of protonation constants from ET-State indices. - Abstract: Tetrapyrrole rings possess four nitrogen atoms, two of which act as Broendsted bases in acidic media. The two protonation steps occur on a close pH range, particularly in the case of meso-tetraphenylporphyrin (TPP) derivatives. If the cause of this phenomenon is well known - a protonation-induced distortion of the porphyrin ring - data on stepwise protonation constants and on electronic absorption spectra of monoprotonated TPPs are sparse. A multivariate approach has been systematically applied to a series of glycoconjugated and hydroxylated TPPs, potential anticancer drugs usable in Photodynamic Therapy. The dual purpose was determination of protonation constants and linking substitution with basicity. Hard-modeling version of MCR-ALS (Multivariate Curve Resolution Alternating Least Squares) has given access to spectra and distribution profile of pure components. Spectra of monoprotonated species (H{sub 3}TPP{sup +}) in solution resemble those of diprotonated species (H{sub 4}TPP{sup 2+}), mainly differing by a slight blue-shift of bands. Overlap of H{sub 3}TPP{sup +} and H{sub 4}TPP{sup 2+} spectra reinforces the difficulty to evidence an intermediate form only present in low relative abundance. Depending on macrocycle substitution, pK values ranged from 3.5 {+-} 0.1 to 5.1 {+-} 0.1 for the first protonation and from 3.2 {+-} 0.2 to 4.9 {+-} 0.1 for the second one. Inner nitrogens' basicity is affected by position, number and nature of peripheral substituents depending on their electrodonating character. pK values have been used to establish a predictive Multiple Linear Regression (MLR) model, relying on atom-type electrotopological indices. This model accurately describes our results and

  10. Activation of electrophilicity of stable Y-delocalized carbamate cations in intramolecular aromatic substitution reaction: evidence for formation of diprotonated carbamates leading to generation of isocyanates.

    Kurouchi, Hiroaki; Kawamoto, Kyoko; Sugimoto, Hiromichi; Nakamura, Satoshi; Otani, Yuko; Ohwada, Tomohiko


    Although cations with three heteroatoms, such as monoprotonated guanidine and urea, are stabilized by Y-shaped conjugation and such Y-conjugated cations are sufficiently basic to be further protonated (or protosolvated) to dications in strongly acid media, only O-monoprotonated species have been detected in the case of carbamates even in magic acid. We found that the trifluoromethanesulfonic acid-catalyzed cyclization of arylethylcarbamates proceeds to afford dihydroisoquinolones in high yield. In strong acids, methyl carbamates are fully O-monoprotonated, and these monocations do not undergo cyclization even under heating. But, as the acidity of the reaction medium is further increased, the cyclization reaction of methyl phenethylcarbamates starts to proceed as a first-order reaction, with a linear relationship between rate and acidity. The sign and magnitude of the entropy of activation ΔS(‡) were found to be similar to those of other A(Ac)1 reactions. These results strongly support the idea that further protonation of the O-protonated carbamates is involved in the cyclization, but the concentration of the dications is very low and suggests that the rate-determining step is dissociation of methanol from the diprotonated carbamate to generate protonated isocyanate, which reacts with the aromatic ring. Therefore, O-protonated carbamates are weak bases in sharp contrast to other Y-shaped monocations.

  11. Structural characterization and physicochemical features of a new arsenate salt templated by mono and di-protonated 4-aminopyridine cations: (C5H7N2)(C5H8N2)[AsO4]·H2O

    Mhadhbi, Noureddine; Naïli, Houcine; Jarraya, Khaled


    Single crystals of a new organic-inorganic hybrid compound, with the formula (4-APH)(4-APH2)[AsO4]·H2O, was synthesized at room temperature by slow evaporation method and characterized by X-ray diffraction at 150 K, DSC-TG measurements, FT-IR and Raman spectroscopies. The title salt, (C5H7N2)(C5H8N2)[AsO4]·H2O, contains mono and diprotonated 4-aminopyridine cations, an arsenate trianion and one water molecule. The diprotonated 4-ammoniumpyridinium dication [C5H8N2]2+ is disordered over two positions with refined site occupancies of 0.73 and 0.27 however the monoprotonated 4-aminopyridinium cation [C5H7N2]+ is ordered. The 4-aminopyridinium rings are essentially planar and occur in stacks along b axis. In the crystal, the AsIII atom is coordinated by four O atoms in a slightly distorted tetrahedral geometry. The arsenate O atoms link the 4-aminopyridinium cations and water molecules into a three-dimensional network via intermolecular O-H···O and N-H···O hydrogen bonds. Additionally, in this structure, the different types and the nature of aromatic-aromatic interactions can distinguish between a stacked arrangement are parallel displaced and T-shaped conformation. Furthermore, the room temperature IR and Raman spectra of the title compound were recorded and analyzed. On the basis of detailed vibrational studies, the detailed assignment confirms the presence of the organic groups and the anionic entities. Besides, the thermal analysis studies have been performed, but no phase transition was found in the temperature range 298-625 K. Results from X-ray crystallography, Raman, IR spectroscopy and thermal analysis are combined to provide a description of the new organic arsenate monohydrate, (C5H7N2)(C5H8N2)[AsO4]·H2O.

  12. Results of search for narrow diproton structures in the pn {yields} pp{pi}{sup -} reaction at 1.98 GeV/c

    Abramov, B.M. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Dukhovskoy, I.A. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Fedorets, V.S. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Khanov, A.I. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Krestnikov, Yu.S. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Krutenkova, A.P. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Kulikov, V.V. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Matsyuk, M.A. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Radkevich, I.A. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Starodumov, A.N. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation); Sutormin, A.I. [Institut Teoreticheskoj i Ehksperimental`noj Fiziki, Moscow (Russian Federation)


    The effective mass spectrum of two protons from the reaction p + n {yields} pp + {pi}{sup -} (backward) was investigated. The work was carried out at ITEP using a 3-meter magnet spectrometer and a proton beam of 1.98 GeV/c momentum. Liquid deuterium was used as a target. The presented mass spectrum includes about 34000 events. No statistically significant signals from narrow dibaryons were found in the mass region 1.89 - 2.17 GeV/c{sup 2}; the upper limits on narrow dibaryon production cross-section are given. At a mass of 1.8775 GeV/c{sup 2} a narrow enhancement was found. A more detailed investigation of the observed phenomenon is needed. (orig.)

  13. Energy dependence of hard bremsstrahlung production in proton-proton collisions in the Delta(1232) region

    Tsirkov, D; Azaryan, T; Chiladze, D; Dymov, S; Dzyuba, A; Hartmann, M; Kacharava, A; Khoukaz, A; Kulikov, A; Kurbatov, V; Macharashvili, G; Merzliakov, S; Mielke, M; Mikirtychiants, S; Nekipelov, M; Rathmann, F; Serdyuk, V; Stroeher, H; Uzikov, Yu; Valdau, Yu; Wilkin, C


    Hard bremsstrahlung production in proton-proton collisions has been studied with the ANKE spectrometer at COSY-Juelich in the energy range of 353-800 MeV by detecting the final proton pair {pp}_s from the pp -> {pp}_s reaction with very low excitation energy. Differential cross sections were measured at small diproton c.m. angles from 0 to 20 degrees and the average over this angular interval reveals a broad peak at a beam energy around 650 MeV with a FWHM of about 220 MeV, suggesting the influence of Delta(1232)N intermediate states. Comparison with deuteron photodisintegration shows that the cross section for diproton production is up to two orders of magnitude smaller, due largely to differences in the selection rules.

  14. 3,12-Diaza-6,9-diazo-nia-2,13-dioxotetra-decane bis-(perchlorate).

    Söhnel, Tilo; Wichmann, Kathrin A; Doert, Thomas; Cooper, Garth J S


    The crystal structure of the title diprotonated diacetyl-triethyl-ene-tetra-mine (DAT) perchorate salt, C(10)H(24)N(4)O(2) (2+)·2ClO(4) (-), can be described as a three-dimensional assembly of alternating layers consisting of diprotonated diacetyl-triethyl-ene-tetra-mine (H(2)DAT)(2+) strands along [100] and the anionic species ClO(4) (-). The (H(2)DAT)(2+) cations in the strands are connected via N-H⋯O hydrogen bonding between the acetyl groups and the amine groups of neighbouring (H(2)DAT)(2+) cations. Layers of (H(2)DAT)(2+) strands and perchlorate anions are connected by a network of hydrogen bonds between the NH and NH(2) groups and the O atoms of the perchlorate anion. The asymmetric unit consits of one perchlorate anion in a general position, as well as of one cation that is located on a center of inversion.

  15. Synthesis of a Chain Aluminophosphate Containing Racemic 1, 2-Diaminopropane


    A one-dimensional chain aluminophosphate C1.5H7.5N1.5Al0.5PO4 containing diprotonated racemic 1, 2-diaminopropane cations was synthesized from an alcoholic system. The compound consists of infinite inorganic [AlP2O8] chains of alternately connected AlO4 and PO2(=O)2 tetrahedral units and the racemic template molecules. The macroanionic chains contain corner-shared double four-membered rings.

  16. Piperazine as counter ion for insulin-enhancing anions [VO2(dipic-OH)]-: Synthesis, characterization and X-ray crystal structure

    Ghasemi, Fatemeh; Ghasemi, Khaled; Rezvani, Ali Reza; Graiff, Claudia


    The new complex [H2Pipz][VO2(dipic-OH)]2·2H2O (1), where H2dipic-OH = 4-hydroxypyridine-2,6-dicarboxylic acid and Pipz = piperazine, was synthesized and characterized by elemental analysis, FTIR, 1H NMR, 13C NMR and UV-Vis spectroscopy and single crystal X-ray diffraction. The crystal system is triclinic with space group Pī. In this compound, piperazine is diprotonated and acts as counter ion.

  17. The origin of the absorption spectra of porphyrin N- and dithiaporphyrin S-oxides in their neutral and protonated states.

    Bruhn, Torsten; Brückner, Christian


    meso-Tetraphenylporphyrin N-oxide (1) and meso-tetraphenyl-21,23-dithiaporphyrin S-oxide (3) possess optical spectra that are distinctly different from their parent porphyrins, meso-tetraphenylporphyrin (2) and meso-tetraphenyl-21,23-dithiaporphyrin (4), respectively. The hyperporphyrin spectra were reproduced and classified using TD CAM-B3LYP and SCS-CC2 computational methods. Calculations revealed the electronic and conformational influences of the N- and S-oxide functionalities. While the N-oxide under acidic conditions forms a dication with a UV-vis spectrum that is nearly indistinguishable from that of the diprotonated parent porphyrin, the diprotonated S-oxide possesses a much different UV-vis spectrum from diprotonated parent dithiaporphyrin. A computational study of the protonation events revealed the site and degree of protonation and rationalized the regular and hyperporphyrin UV-vis spectra of the neutral and protonated species, respectively. The study illuminates the electronic effects of the relatively rare modification of the inner porphyrin heteroatoms. It also illustrates a case in which TD CAM-B3LYP reaches its limits to make reliable predictions about the optical properties of a porphyrinoid, making the use of higher methods essential.

  18. Mechanisms of HNO and NO production from Angeli's salt: density functional and CBS-QB3 theory predictions.

    Dutton, Andrew S; Fukuto, Jon M; Houk, K N


    The mechanism of decomposition of Angeli's salt, Na(2)N(2)O(3), was explored with B3LYP and CBS-QB3 computational methods. Angeli's salt produces both nitroxyl (HNO) and nitric oxide (NO), depending upon the pH of the solution. These calculations show that protonation on N(2), while less favorable than O protonation, leads spontaneously to HNO production, while diprotonation at O(3) leads to NO generation. K(a) values for protonation at different centers and rate constants have been found which reproduce experimental data satisfactorily.

  19. 2,4,6-Triamino-1,3,5-triazine-1,3-diium aquapentafluoridoaluminate

    V. Maisonneuve


    Full Text Available The title compound, (C3H8N6[AlF5(H2O], was obtained by solvothermal synthesis from the reaction of aluminium hydroxide, 1,3,5-triazine-2,4,6-triamine (melamine, aqueous HF and water at 323 K for 48 h. The structure consists of [AlF5(H2O]2− octahedra and diprotonated melaminium cations. Cohesion is ensured by a three-dimensional network of hydrogen bonds.

  20. Experimental Evidence of Two-Proton Emissions from lSNe Excited State

    JIA Fei; LIN Cheng-Jian; ZHANG Huan-Qiao; YANG Feng; JIA Hui-Ming; XU Xin-Xing; WU Zhen-Dong; LIU Zu-Hua; ZHANG Gao-Long; ZHANG Chun-Lei


    Experiment 18 Ne+197 Au was performed in Heavy Ion Research Facility Radioactive Ion Beam Line at Lanzhou (RIBLL).The nuclear energy levels of 18 Ne were built by complete kinematical reconstruction of the decay products and diproton decay were observed from 18 Ne excited states.At 6.15 MeV,the experimental relative momentum and angular correlations of the emitted protons are given. The obvious enhancement at |qrel| =23 MeV/c and θc.m.= 40° shows the experimental criterion of 2 He duster decay from 18 Neq.

  1. Crystal and molecular structure of 2,2'-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H2 L)(NO3)2

    Egorova, O. A.; Polyakova, I. N.; Sergienko, V. S.; Davydov, V. V.


    The crystal structure of 2,2'-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H2 L)(NO3)2 is studied by X-ray diffraction ( T = 150 K, R1 = 0.0467). The H2 L 2+ cation is located on the twofold rotation axis and connected with two NO3 - anions by strong N-H···O hydrogen bonds. Planar quinoxaline fragments of cations form stacks with the interplanar spacing of 3.308 Å. The structure of the diprotonated H2 L 2+ cation is compared with those of the monoprotonated H2 L 2+ cation and neutral L molecule.

  2. Enhanced Anion Transport Using Some Expanded Porphyrins as Carriers.


    step, an acid catalyzed 1: 1 Schiff - base condensation between I ,8-diaminoanthracene 4 and 2,5-bis((3-ethylS_-formyl-4- methy’lpyrrol-2-yl) methyl... Schiff base "expanded porphyrin," 1, which when diprotonated effectively binds chloride anion in the solid state.8- 10 In addition, we present the results...parent, 1, is shown in Scheme 1. It involves, as the critical step, the acid catalyzed 1:1 Schiff - base condensation between 1.8-diaminoanthracene 49

  3. Selenium dioxide catalysed oxidation of acetic acid hydrazide by bromate in aqueous hydrochloric acid medium

    R S Yalgudre; G S Gokavi


    Selenium dioxide catalysed acetic acid hydrazide oxidation by bromate was studied in hydrochloric acid medium. The order in oxidant concentration, substrate and catalyst were found to be unity. Increasing hydrogen ion concentration increases the rate of the reaction due to protonation equilibria of the oxidant. The mechanism of the reaction involves prior complex formation between the catalyst and substrate, hydrazide, followed by its oxidation by diprotonated bromate in a slow step. Acetic acid was found to be the oxidation product. Other kinetic data like effect of solvent polarity and ionic strength on the reaction support the proposed mechanism.

  4. Shell model with several particles in the continuum: application to the two-proton decay; Modele en couches avec plusieurs particules dans le continuum: description de la radioactivite deux protons

    Rotureau, J


    The recent experimental results concerning nuclei at the limit of stability close to the drip-lines and in particular the two-proton emitters require a development of new methodologies to reliably calculate and understand properties of those exotic physical systems. In this work we have extended the Shell Model Embedded in the Continuum (SMEC) in order to describe the coupling with two particles in the scattering continuum. We have obtained a microscopic description of the two-proton emission that takes into account the antisymmetrization of the total wavefunction, the configuration mixing and the three-body asymptotics. We have studied the decay of the 1{sub 2}{sup -} state in {sup 18}Ne in two limiting cases: (i) a sequential emission of two protons through the correlated continuum of {sup 17}F and (ii) emission of {sup 2}He cluster that disintegrates because of the final state interaction (diproton emission). Independently of the choice of the effective interaction we have observed that the two-proton emission of the 1{sub 2}{sup -} in {sup 18}Ne is mainly a sequential process; the ratio between the widths of the diproton emission and the sequential decay does not exceed 8% in any case. (author)

  5. Analysis by partial reflection spectrometry of protonated tetraphenylporphyrin adsorbed at a liquid-liquid interface.

    Moriya, Yoshio; Hasegawa, Takeshi; Hayashi, Kotaro; Maruyama, Machiko; Nakata, Shinichi; Ogawa, Nobuaki


    Visible reflection spectra of diprotonated meso-tetraphenylporphyrin adsorbates spontaneously formed at a dodecane-aqueous sulfuric acid interface have been measured using a home-made device comprising a prism-cell and variable-angle optics. The tilt angle of the pyrrole ring plane was estimated to be 47 degrees from the interface normal by use of an experimentally evaluated molecular density (1.20x10(-10) mol cm(-2)) of the diprotonated molecule in a monolayer form at the liquid-liquid interface. Positive and negative bands have been observed in the p-polarized partial internal reflection (p-PIR) spectra, whose band locations correspond to those in p-polarized external reflection (p-ER) spectra. Nevertheless, the bands in the p-PIR exhibited reversed sign to those of p-ER spectra. These suggest that the surface selection rule of the p-PIR spectrometry has a reversal rule of p-ER and p-PIR can also be used for the analysis of molecular orientation.

  6. Poly[[2-(3-pyridinio-1H,3H+-benzimidazolium] [μ4-oxido-di-μ3-oxido-tetra-μ2-oxido-hexaoxidotetramolybdenum(VI

    Xiao-Hua Chen


    Full Text Available The reaction of MoO3 with 2-(3-pyridylbenzoimidazole and water in the presence of MnSO4·5H2O at 453 K under hydrothermal conditions afforded the title compound, {(C12H11N2[Mo4O13]}n, in which infinite molybdenum oxide anionic chains are charge-balanced by diprotonated 2-(3-pyridylbenzoimidazole (H23-PBIM2+ cations. Eight [MoO6] octahedra are edge-shared, forming compact octamolybdate subunits which are connected through pairs of Mo—O—Mo bridges into extended one-dimensional arrays propagating along the a-axis direction. The asymmetric unit of the metal oxide chain contains one half of the octamolybdate unit, denoted [Mo4O13], the other half being generated by an inversion center. These molybdenum oxide chains are further connected through the 2-(3-pyridiniobenzoimidazolium cations into a three-dimensional network via N—H...O hydrogen bonds. In addition, neighbouring diprotonated cations are arranged in a head-to-tail fashion with a plane-to-plane separation of 3.63 (10 Å, indicating the existence of weak aromatic π–π stacking interactions.

  7. Dinucleon correlation of $^9$Li, $^{10}$Be, and $^{9,10}$C

    Kobayashi, Fumiharu


    We study the dinucleon (dineutron and diproton) correlation of the ground states of $^9$Li, $^{10}$Be, and $^{9,10}$C. We assume an $\\alpha+t$ core for $^9$Li, an $\\alpha+\\alpha$ core for $^{10}$Be and $^{10}$C, and an $\\alpha+^3$He core for $^9$C, and investigate the effect of core structure changes on the degree of dineutron formation and spatial expansion from the core. For $^9$Li, $t$ cluster breaking in the core significantly enhances the dineutron component inside the nuclei. Moreover, its component markedly depends on the strength of the spin-orbit interaction since a dineutron is fragile and dissociates readily due to the spin-orbit interaction. Compared with $^9$Li, the dineutron of $^{10}$Be dissociates largely due to the stronger spin-orbit attraction from the $\\alpha+\\alpha$ core than the $\\alpha+t$ core. We also investigate diproton features in $^{9,10}$C, the mirror nuclei of $^9$Li and $^{10}$Be, respectively, and compare them with the dineutron features of $^9$Li and $^{10}$Be. No qualitative ...

  8. Excitation of the Delta(1232) isobar in deuteron charge exchange on hydrogen at 1.6, 1.8, and 2.3 GeV

    Mchedlishvili, D; Carbonell, J; Chiladze, D; Dymov, S; Dzyuba, A; Engels, R; Gebel, R; Glagolev, V; Grigoryev, K; Goslawski, P; Hartmann, M; Imambekov, O; Kacharava, A; Kamerdzhiev, V; Keshelashvili, I; Khoukaz, A; Komarov, V; Kulessa, P; Kulikov, A; Lehrach, A; Lomidze, N; Lorentz, B; Macharashvili, G; Maier, R; Merzliakov, S; Mielke, M; Mikirtychyants, M; Mikirtychyants, S; Nioradze, M; Ohm, H; Papenbrock, M; Prasuhn, D; Rathmann, F; Serdyuk, V; Seyfarth, H; Stein, H J; Steffens, E; Stockhorst, H; Ströher, H; Tabidze, M; Trusov, S; Uzikov, Yu; Valdau, Yu; Wilkin, C


    The charge-exchange break-up of polarised deuterons pol{d}p -> {pp}n, where the final {pp} diproton system has a very low excitation energy and hence is mainly in the 1S0 state, is a powerful tool to probe the spin-flip terms in the proton-neutron charge-exchange scattering. Recent measurements with the ANKE spectrometer at the COSY storage ring at 1.6, 1.8, and 2.27 GeV have extended these studies into the pion-production regime in order to investigate the mechanism for the excitation of the Delta(1232) isobar in the pol{d}p -> {pp}X reaction. Values of the differential cross section and two deuteron tensor analysing powers, A_{xx} and A_{yy}, have been extracted in terms of the momentum transfer to the diproton or the invariant mass Mx of the unobserved system X. The unpolarised cross section in the high Mx region is well described in a model that includes only direct excitation of the Delta isobar through undistorted one pion exchange. However, the cross section is grossly underestimated for low Mx, even w...

  9. Differential cross section and analysing power of the pp -> {pp\\}_s pi0 reaction at 353 MeV

    Tsirkov, D; Baru, V; Chiladze, D; Dymov, S; Dzyuba, A; Gebel, R; Goslawski, P; Hanhart, C; Hartmann, M; Kacharava, A; Khoukaz, A; Komarov, V; Kulessa, P; Kulikov, A; Kurbatov, V; Lensky, V; Lorentz, B; Macharashvili, G; Mchedslishvili, D; Mielke, M; Mikirtytchiants, S; Merzliakov, S; Nioradze, M; Ohm, H; Papenbrock, M; Rathmann, F; Serdyuk, V; Shmakova, V; Stroeher, H; Uzikov, Yu; Valdau, Yu; Wilkin, C


    In order to establish links between p-wave pion production in nucleon-nucleon collisions and low energy three-nucleon scattering, an extensive programme of experiments on pion production is currently underway at COSY-ANKE. The final proton pair is detected at very low excitation energy, leading to an S-wave diproton, denoted here as {pp}_s. We now report on measurements of the differential cross section and analysing power of the pol{p}p->{pp}_s pi^0$ reaction at 353 MeV. Both observables can be described in terms of s- and d-wave pion production and, by using the phase information from elastic pp scattering, unique solutions can be obtained for the corresponding amplitudes. This information is vital for the partial wave decomposition of the corresponding pn->{pp}_s pi^- reaction and hence for the extraction of the p-wave terms.

  10. Observation of an ABC effect in proton-proton collisions

    Dymov, S; Kacharava, A; Khoukaz, A; Komarov, V; Kulessa, P; Kulikov, A; Kurbatov, V; Macharashvili, G; Merzliakov, S; Mielke, M; Mikirtychiants, S; Nekipelov, M; Nioradze, M; Ohm, H; Rathmann, F; Ströher, H; Tsirkov, D; Uzikov, Yu; Valdau, Yu; Wilkin, C; Yaschenko, S; Zalikhanov, B


    The cross section for inclusive multipion production in the pp->ppX reaction was measured at COSY-ANKE at four beam energies, 0.8, 1.1, 1.4, and 2.0 GeV, for low excitation energy in the final pp system, such that the diproton quasi-particle is in the 1S0 state. At the three higher energies the missing mass Mx spectra show a strong enhancement at low Mx, corresponding to an ABC effect that moves steadily to larger values as the energy is increased. Despite the missing-mass structure looking very different at 0.8 GeV, the variation with Mx and beam energy are consistent with two-pion production being mediated through the excitation of two Delta(1232) isobars, coupled to S-- and D-- states of the initial pp system.

  11. Analysing powers and spin correlations in deuteron–proton charge exchange at 726 MeV

    S. Dymov


    Full Text Available The charge exchange of vector polarised deuterons on a polarised hydrogen target has been studied in a high statistics experiment at the COSY-ANKE facility at a deuteron beam energy of Td=726 MeV. By selecting two fast protons at low relative energy Epp, the measured analysing powers and spin correlations are sensitive to interference terms between specific neutron–proton charge-exchange amplitudes at a neutron kinetic energy of Tn≈12Td=363 MeV. An impulse approximation calculation, which takes into account corrections due to the angular distribution in the diproton, describes reasonably the dependence of the data on both Epp and the momentum transfer. This lends broad support to the current neutron–proton partial wave solution that was used in the estimation.

  12. Different mechanism of two-proton emission from proton-rich nuclei $^{23}$Al and $^{22}$Mg

    Ma, Y G; Sun, X Y; Zhou, P; Togano, Y; Aoi, N; Baba, H; Cai, X Z; Cao, X G; Chen, J G; Fu, Y; Guo, W; Hara, Y; Honda, T; Hu, Z G; Ieki, K; Ishibashi, Y; Ito, Y; Iwasa, N; Kanno, S; Kawabata, T; Kimura, H; Kondo, Y; Kurita, K; Kurokawa, M; Moriguchi, T; Murakami, H; Ooishi, H; Okada, K; Ota, S; Ozawa, A; Sakurai, H; Shimoura, S; Shioda, R; Takeshita, E; Takeuchi, S; Tian, W D; Wang, H W; Wang, J S; Wang, M; Yamada, K; Yamada, Y; Yasuda, Y; Yoneda, K; Zhang, G Q; Motobayashi, T


    Two-proton relative momentum ($q_{pp}$) and opening angle ($\\theta_{pp}$) distributions from the three-body decay of two excited proton-rich nuclei, namely $^{23}$Al $\\rightarrow$ p + p + $^{21}$Na and $^{22}$Mg $\\rightarrow$ p + p + $^{20}$Ne, have been measured with the projectile fragment separator (RIPS) at the RIKEN RI Beam Factory. An evident peak at $q_{pp}\\sim20$ MeV/c as well as a peak in $\\theta_{pp}$ around 30$^\\circ$ are seen in the two-proton break-up channel from a highly-excited $^{22}$Mg. In contrast, such peaks are absent for the $^{23}$Al case. It is concluded that the two-proton emission mechanism of excited $^{22}$Mg is quite different from the $^{23}$Al case, with the former having a favorable diproton emission component at a highly excited state and the latter dominated by the sequential decay process.

  13. Beta-alanine-oxalic acid (1:1) hemihydrate crystal: structure, 13C NMR and vibrational properties, protonation character.

    Godzisz, D; Ilczyszyn, M; Ilczyszyn, M M


    The crystal structure of beta-alanine-oxalic acid (1:1) hemihydrate complex has been reinvestigated by X-ray diffraction method at 293 K. Formation of monoclinic crystal system belonging to C2/c space group and consisting of semi-oxalate chains, diprotonated beta-alanine dimers and water molecules bonded to both these units is confirmed. New results are obtained for distances in the carboxylic groups and hydrogen bonds. These structural observations are used for protonation degree monitoring on the carboxylic oxygen atoms. They are in accordance with our vibrational study. The 13C NMR spectra provide insights into the solid structure of this complex, character of its hydrogen bonds and the beta-alanine protonation.

  14. Electrochemistry of hexanitroazobenzene: reactivity with metals and synthetic implications

    Firsich, D.W.


    The electrochemical properties of hexanitroazobenzene (HNAB) are defined as an aid towards understanding the general reactivity of this commonly used explosive. Cyclic voltammetry, controlled potential coulometry, and visible spectroscopy are used to characterize the anion, dianion, protonated dianion, and diprotonated dianion of HNAB. The acid/base relationships of these species are established, and their role in the present synthetic method for producing HNAB is clearly defined. The feasibility of an electrochemical synthesis for HNAB is demonstrated. It is shown that the reaction between aluminum metal and HNAB in solution produces the protonated dianion of HNAB, and that reactions between other common metals and HNAB do occur. The visible absorption maxima of a number of possible decomposition products of HNAB are compiled. Related chemistry involving a triazole oxide derivative is presented. 5 refs., 5 figs., 2 tabs.

  15. Quantization of second-order Lagrangians: The Fokker-Wheeler-Feynman model of electrodynamics

    Moore, R. A.; Scott, T. C.


    The consequences of quantizing the Fokker-Wheeler-Feynman model of electrodynamics, treating the Lagrangian via its acceleration-dependent (1/c) power-series representation, is examined using recently validated methods. An exact treatment of this acceleration dependence yields, under certain circumstances, high-energy resonant modes. In the past, such modes have been assumed unphysical and have been removed by perturbative or order-reduction techniques. However, these modes appear to be of physical significance. This conclusion follows because this completely ab initio calculation, with no adjustable parameters, has a number of successes. It provides a description for resonances observed in the electron-positron emission from heavy-ion collisions, in particular, and in diproton collisions and, possibly, in other collision experiments as well.

  16. Analysing powers and spin correlations in deuteron-proton charge exchange at 726 MeV

    Dymov, S; Bagdasarian, Z; Barsov, S; Carbonell, J; Chiladze, D; Engels, R; Gebel, R; Grigoryev, K; Hartmann, M; Kacharava, A; Khoukaz, A; Komarov, V; Kulessa, P; Kulikov, A; Kurbatov, V; Lomidze, N; Lorentz, B; Macharashvili, G; Mchedlishvili, D; Merzliakov, S; Mielke, M; Mikirtychyants, M; Mikirtychyants, S; Nioradze, M; Ohm, H; Prasuhn, D; Rathmann, F; Serdyuk, V; Seyfarth, H; Shmakova, V; Ströher, H; Tabidze, M; Trusov, S; Tsirkov, D; Uzikov, Yu; Valdau, Yu; Weidemann, C; Wilkin, C


    The charge exchange of vector polarised deuterons on a polarised hydrogen target has been studied in a high statistics experiment at the COSY-ANKE facility at a deuteron beam energy of Td = 726 MeV. By selecting two fast protons at low relative energy E_{pp}, the measured analysing powers and spin correlations are sensitive to interference terms between specific neutron-proton charge-exchange amplitudes at a neutron kinetic energy of Tn ~ 1/2 Td =363 MeV. An impulse approximation calculation, which takes into account corrections due to the angular distribution in the diproton, describes reasonably the dependence of the data on both E_{pp} and the momentum transfer. This lends broad support to the current neutron-proton partial-wave solution that was used in the estimation.

  17. 1-(2-Hydroxyethyl-4-{3-[(E-2-(trifluoromethyl-9H-thioxanthen-9-ylidene]propyl}piperazine-1,4-diium bis(3-carboxyprop-2-enoate

    M. S. Siddegowda


    Full Text Available In the title salt, C23H27F3N2OS+·2C4H3O4−, a non-merohedral twin [ratio of the twin components = 0.402 (1:0.598 (1], the –CF3 group is disordered over two sets of sites with occupancy factors in the ratio 0.873 (2:0.127 (2. The dihedral angle between the two outer aromatic rings of the 9H-thioxanthene unit, whose thiopyran ring has a screw-boat conformation, is 33.01 (9°. The diprotonated piperazine ring adopts a chair conformation. In the crystal, intermolecular O—H...O, N—H...O and C—H...O hydrogen bonds between neighboring molecules form zigzag chains along the a axis and contribute to the stabilization of the packing.

  18. Single-Step Access to Long-Chain α,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acids

    Goldbach, Verena


    Dicarboxylic acids are compounds of high value, but to date long-chain alpha,omega-dicarboxylic acids have been difficult to access in a direct way. Unsaturated fatty acids are ideal starting materials with their molecular structure of long methylene sequences and a carboxylate functionality, in addition to a double bond that offers itself for functionalization. Within this paper, we established a direct access to alpha,omega-dicarboxylic acids by combining isomerization and selective terminal carbonylation of the internal double bond with water as a nucleophile on unsaturated fatty acids. We identified the key elements of this reaction: a homogeneous reaction mixture ensuring sufficient contact between all reactants and a catalyst system allowing for activation of the Pd precursor under aqueous conditions. Experiments under pressure reactor conditions with [(dtbpx)Pd(OTf)(2)] as catalyst precursor revealed the importance of nucleophile and reactant concentrations and the addition of the diprotonated diphosphine ligand (dtbpxH(2))(OTf)(2) to achieve turnover numbers >120. A variety of unsaturated fatty acids, including a triglyceride, were converted to valuable long-chain dicarboxylic acids with high turnover numbers and selectivities for the linear product of >90%. We unraveled the activation pathway of the Pd-II precursor, which proceeds via a reductive elimination step forming a Pd species and oxidative addition of the diprotonated diphosphine ligand, resulting in the formation of the catalytically active Pd hydride species. Theoretical calculations identified the hydrolysis as the rate-determining step. A low nucleophile concentration in the reaction mixture in combination with this high energetic barrier limits the potential of this reaction. In conclusion, water can be utilized as a nucleophile in isomerizing functionalization reactions and gives access to long-chain dicarboxylic acids from a variety of unsaturated substrates. The activity of the catalytic

  19. Excitation of the Δ(1232) isobar in deuteron charge exchange on hydrogen at 1.6, 1.8, and 2.3 GeV

    Mchedlishvili, D. [High Energy Physics Institute, Tbilisi State University, GE-0186 Tbilisi, Georgia (United States); Institut für Kernphysik and Jülich Centre for Hadron Physics, Forschungszentrum Jülich, D-52425 Jülich (Germany); Barsov, S. [High Energy Physics Department, Petersburg Nuclear Physics Institute, RU-188350 Gatchina (Russian Federation); Carbonell, J. [Institut de Physique Nucléaire, Université Paris-Sud, IN2P3-CNRS, F-91406 Orsay Cedex (France); Chiladze, D. [High Energy Physics Institute, Tbilisi State University, GE-0186 Tbilisi, Georgia (United States); Institut für Kernphysik and Jülich Centre for Hadron Physics, Forschungszentrum Jülich, D-52425 Jülich (Germany); Dymov, S. [Laboratory of Nuclear Problems, JINR, RU-141980 Dubna (Russian Federation); Physikalisches Institut II, Universität Erlangen-Nürnberg, D-91058 Erlangen (Germany); Dzyuba, A. [High Energy Physics Department, Petersburg Nuclear Physics Institute, RU-188350 Gatchina (Russian Federation); Engels, R.; Gebel, R. [Institut für Kernphysik and Jülich Centre for Hadron Physics, Forschungszentrum Jülich, D-52425 Jülich (Germany); Glagolev, V. [Laboratory of High Energies, JINR, RU-141980 Dubna (Russian Federation); and others


    The charge-exchange break-up of polarised deuterons d{sup →}p→{pp}{sub s}n, where the final {pp}{sub s} diproton system has a very low excitation energy and hence is mainly in the {sup 1}S{sub 0} state, is a powerful tool to probe the spin-flip terms in the proton–neutron charge-exchange scattering. Recent measurements with the ANKE spectrometer at the COSY storage ring at 1.6, 1.8, and 2.27 GeV have extended these studies into the pion-production regime in order to investigate the mechanism for the excitation of the Δ(1232) isobar in the d{sup →}p→{pp}{sub s}X reaction. Values of the differential cross section and two deuteron tensor analysing powers, A{sub xx} and A{sub yy}, have been extracted as functions of the momentum transfer to the diproton or the invariant mass M{sub X} of the unobserved system X. The unpolarised cross section in the high M{sub X} region is well described in a model that includes only direct excitation of the Δ isobar through undistorted one pion exchange. However, the cross section is grossly underestimated for low M{sub X}, even when Δ excitation in the projectile deuteron is included in the calculation. Furthermore, direct Δ production through one pion exchange only reproduces the angular dependence of the difference between the two tensor analysing powers.

  20. Analyzing Powers and Differential Cross Sections for Polarized Proton Neutron Going to Negative Pion Proton Proton

    Duncan, Fraser Andrew

    There is considerable interest in the pn to pi^-pp reaction which can proceed by a nonresonant channel from the isospin 0 pn initial state (an NDelta intermediate state cannot be formed). This thesis describes a measurement of analyzing powers and triple differential cross sections for a subset of this reaction, pn to pi^-pp(^1S_0) by isolating the quasifree process in pd to pi^-ppp_{s}. The experimental arrangement selects the relative S-wave component of the outgoing "diproton". The experiment was done on TRIUMF beam line 1B using a LD_2 target; the pion was detected in a magnetic spectrometer, the two outgoing protons in a scintillator bar array. The spectator proton was undetected. Data were taken in August 1989 at 353, 403 and 440 MeV beam energies. Of these the 403 and 440 MeV data are analysed in this thesis and analyzing powers and triple differential cross sections as a function of pion scattering angle extracted at centre of mass kinetic energies, T_{CM}, of 55 and 70 MeV (corresponding to the 403 and 440 MeV beam energies respectively). Partial wave analysis of the data shows that, while the isospin 0 channel dominates the reaction, contributing approximately 75% of the cross section at the energies studied here, there are significant contributions from the s and d-wave pion, isospin 1 channels. Of particular importance is the contribution from the s-wave pion, isospin 1, channel whose interference with the isospin 0 channels produces the characteristic shapes of the cross sections and analyzing powers observed in the data. The d-wave pion, isospin 1 channels, are also required to fully explain the observed analyzing power distributions, and are essential for the T_{CM} = 70MeV data. Comparisons of the pion production data measured in this experiment with pion absorption measurements on ^3He, where the absorption process is pi^-pp(^1S_0) to pn, show a shift in the shape of the differential cross section which can be interpreted as due to differences in

  1. Photocatalytic Oxygenation of Substrates by Dioxygen with Protonated Manganese(III) Corrolazine.

    Jung, Jieun; Neu, Heather M; Leeladee, Pannee; Siegler, Maxime A; Ohkubo, Kei; Goldberg, David P; Fukuzumi, Shunichi


    UV-vis spectral titrations of a manganese(III) corrolazine complex [Mn(III)(TBP8Cz)] with HOTf in benzonitrile (PhCN) indicate mono- and diprotonation of Mn(III)(TBP8Cz) to give Mn(III)(OTf)(TBP8Cz(H)) and [Mn(III)(OTf)(H2O)(TBP8Cz(H)2)][OTf] with protonation constants of 9.0 × 10(6) and 4.7 × 10(3) M(-1), respectively. The protonated sites of Mn(III)(OTf)(TBP8Cz(H)) and [Mn(III)(OTf)(H2O)(TBP8Cz(H)2)][OTf] were identified by X-ray crystal structures of the mono- and diprotonated complexes. In the presence of HOTf, the monoprotonated manganese(III) corrolazine complex [Mn(III)(OTf)(TBP8Cz(H))] acts as an efficient photocatalytic catalyst for the oxidation of hexamethylbenzene and thioanisole by O2 to the corresponding alcohol and sulfoxide with 563 and 902 TON, respectively. Femtosecond laser flash photolysis measurements of Mn(III)(OTf)(TBP8Cz(H)) and [Mn(III)(OTf)(H2O)(TBP8Cz(H)2)][OTf] in the presence of O2 revealed the formation of a tripquintet excited state, which was rapidly converted to a tripseptet excited state. The tripseptet excited state of Mn(III)(OTf)(TBP8Cz(H)) reacted with O2 with a diffusion-limited rate constant to produce the putative Mn(IV)(O2(•-))(OTf)(TBP8Cz(H)), whereas the tripseptet excited state of [Mn(III)(OTf)(H2O)(TBP8Cz(H)2)][OTf] exhibited no reactivity toward O2. In the presence of HOTf, Mn(V)(O)(TBP8Cz) can oxidize not only HMB but also mesitylene to the corresponding alcohols, accompanied by regeneration of Mn(III)(OTf)(TBP8Cz(H)). This thermal reaction was examined for a kinetic isotope effect, and essentially no KIE (1.1) was observed for the oxidation of mesitylene-d12, suggesting a proton-coupled electron transfer (PCET) mechanism is operative in this case. Thus, the monoprotonated manganese(III) corrolazine complex, Mn(III)(OTf)(TBP8Cz(H)), acts as an efficient photocatalyst for the oxidation of HMB by O2 to the alcohol.

  2. Study of the $\\vec{p}d \\to n\\{pp\\}_{s}$ charge-exchange reaction using a polarised deuterium target

    Gou, B; Bagdasarian, Z; Barsov, S; Chiladze, D; Dymov, S; Engels, R; Gaisser, M; Gebel, R; Grigoryev, K; Hartmann, M; Kacharava, A; Khoukaz, A; Kulessa, P; Kulikov, A; Lehrach, A; Li, Z; Lomidze, N; Lorentz, B; Macharashvili, G; Merzliakov, S; Mielke, M; Mikirtychyants, M; Mikirtychyants, S; Nioradze, M; Ohm, H; Prasuhn, D; Rathmann, F; Serdyuk, V; Seyfarth, H; Shmakova, V; Ströher, H; Tabidze, M; Trusov, S; Tsirkov, D; Uzikov, Yu; Valdau, Yu; Wang, T; Weidemann, C; Wilkin, C; Yuan, X


    The vector and tensor analysing powers, $A_y$ and $A_{yy}$, of the $\\vec{p}d \\to n\\{pp\\}_{s}$ charge-exchange reaction have been measured at a beam energy of 600 MeV at the COSY-ANKE facility by using an unpolarised proton beam incident on an internal storage cell target filled with polarised deuterium gas. The low energy recoiling protons were measured in a pair of silicon tracking telescopes placed on either side of the target. Putting a cut of 3 MeV on the diproton excitation energy ensured that the two protons were dominantly in the $^{1}S_{0}$ state, here denoted by $\\{pp\\}_{s}$. The polarisation of the deuterium gas was established through measurements in parallel of proton-deuteron elastic scattering. By analysing events where both protons entered the same telescope, the charge-exchange reaction was measured for momentum transfers $q\\geq 160$ MeV/$c$. These data provide a good continuation of the earlier results at $q\\leq 140$ MeV/$c$ obtained with a polarised deuteron beam. They are also consistent wi...

  3. Study of the pd→→n{pp}s charge-exchange reaction using a polarised deuterium target

    B. Gou


    Full Text Available The vector and tensor analysing powers, Ay and Ayy, of the pd→→n{pp}s charge-exchange reaction have been measured at a beam energy of 600 MeV at the COSY-ANKE facility by using an unpolarised proton beam incident on an internal storage cell target filled with polarised deuterium gas. The low energy recoiling protons were measured in a pair of silicon tracking telescopes placed on either side of the target. Putting a cut of 3 MeV on the diproton excitation energy ensured that the two protons were dominantly in the S01 state, here denoted by {pp}s. The polarisation of the deuterium gas was established through measurements in parallel of proton–deuteron elastic scattering. By analysing events where both protons entered the same telescope, the charge-exchange reaction was measured for momentum transfers q≥160 MeV/c. These data provide a good continuation of the earlier results at q≤140 MeV/c obtained with a polarised deuteron beam. They are also consistent with impulse approximation predictions with little sign evident for any modifications due to multiple scatterings. These successful results confirm that the ANKE deuteron charge-exchange programme can be extended to much higher energies with a polarised deuterium target than can be achieved with a polarised deuteron beam.

  4. Differential cross section and analysing power of the quasi-free pn -> {pp}_s pi- reaction at 353 MeV

    Dymov, S; Barsov, S; Baru, V; Benati, P; Bertelli, S; Chiladze, D; Dzyuba, A; Gebel, R; Goslawski, P; Guidoboni, G; Hanhart, C; Hartmann, M; Kacharava, A; Khoukaz, A; Komarov, V; Kulessa, P; Kulikov, A; Kurbatov, V; Lenisa, P; Lensky, V; Lomidze, N; Lorentz, B; Macharashvili, G; Mielke, M; Mikirtytchiants, S; Merzliakov, S; Ohm, H; Papenbrock, M; Rathmann, F; Serdyuk, V; Shmakova, V; Stroeher, H; Tabidze, M; Tsirkov, D; Trusov, S; Uzikov, Yu; Valdau, Yu; Wilkin, C


    In order to establish links between p-wave pion production in nucleon-nucleon collisions and low energy three-nucleon scattering, an extensive programme of experiments on pion production is currently underway at COSY-ANKE. The final proton pair is measured at very low excitation energy, leading to an S-wave diproton, denoted here as {pp}_s. By using a deuterium target we have obtained data on the differential cross section and analysing power of the quasi-free pol{p}n -> {pp}_s pi^- reaction at 353 MeV. The spectator proton p_sp was either measured directly in silicon tracking telescopes or reconstructed using the momentum of a detected pi^-. Both observables can be described in terms of s-, p-, and d-wave pion production amplitudes. Taken together with the analogous data on the pol{p}p -> {pp}_s pi^0 reaction, full partial wave decompositions of both processes were carried out.

  5. ACO-zeotype iron aluminum phosphates with variable Al/Fe ratios controlled by F⁻ ions.

    Wang, Yanyan; Li, Yi; Wang, Lei; Zhang, Jingzhe; Yan, Yan; Li, Jiyang; Yu, Jihong; Wang, Jincheng; Xu, Ruren


    Three new iron aluminum phosphates |(C(2)H(10)N(2))(4)|[Fe(8 - x)Al(x)F(x)(H(2)O)(2 - x)(PO(4))(8)]·2H(2)O (χ = 1.64, 1.33, 0.80) with ACO-zeotype structures denoted as FeAPO-CJ66(a), FeAPO-CJ66(b), and FeAPO-CJ66(c), respectively, have been synthesized in the fluoride ion system. Their framework structures are made of double 4-ring (D4R) building units formed by the alternating connection of Fe(Al)O(4)F(O) trigonal bipyramids and PO(4) tetrahedra, which possess 3D intersecting 8-ring channels running along the [001], [010], and [100] directions. Fluoride ions or water molecules reside in the center of D4Rs, and diprotonated ethylenediamine cations and water molecules are occluded in the free space of channels to stabilize the whole structure. Notably, the Al/Fe ratios in the frameworks can be effectively controlled from 1/3.9 to 1/5.0 to 1/9.0 by adjusting the amounts of phosphoric acid and hydrofluoric acid added to the initial reaction mixture. Mössbauer and magnetic measurements show that the Fe ions in the compounds are bivalent and undergo antiferromagnetic ordering at room temperature.

  6. Experimental research into the two-proton emissions from 17,18 Ne,28 P and 28,29S


    Two-proton emissions from the excited states of 17,18Ne, 28P and 28,29S were investigated experimentally by the radioactive beams bombarding on the 197Au target via the Coulomb excitation. The complete-kinematics measurements were actualized by the stacks of silicon-strip detectors and CsI+PIN array detectors. The invariant mass of final systems as well as the relative momentum, opening angle, and relative energy of the two emitted protons was reconstructed under the framework of relativ istic kinematics. Visible proton-proton correlations were observed in these systems. The mechanisms of two-proton emission were analyzed in a simple schematic model, in which the extreme decay modes like He cluster emission, three-body 2 phase-space decay, and two-body sequential decay were taken into account. With the help of Monte-Carlo simulations, the two protons emitted from the 6.15 MeV excited state of Ne and the excited states in the energy region of 9.6–10.4 MeV of S, 18 29 respectively, exhibited prominent features of2 He cluster decay while for the other cases, no obvious diproton emissions were observed.

  7. Dissolution of copper phthalocyanine and fabrication of its nano-structure film


    The mono-protonated and di-protonated forms of copper phthalocyanine (CuPc) were obtained by increasing concentrations of trifluoroacetic acid (TFA) solution to a fixed concentration of CuPc solutions. UV-Vis spectrum shows that the Q bands of these two derivatives split and shift to the red, which means successive protonation happened and caused the two derivatives to lose their symmetry. After the protonation step, the solubility of protonated CuPc in organic solvent increased 60 times. The CuPc film was fabricated by the electrophoretic deposition (EPD) method from the protonated CuPc dissolved in nitromethane containing TFA. Scanning electron microscopy (SEM) showed that the deposited CuPc film on the indium tin oxide (ITO) substrate is composed of thread-like nanobelts with diameters between 100 nm and 200 nm. Furthermore, the CuPc film is in α phase with stacking direction (b-axis) parallel to the substrate, which was detected by X-ray diffraction.

  8. Dissolution of copper phthalocyanine and fabrication of its nano-structure film

    SU JinLi; XUE MinZhao; MA Ning; SHENG QiaoRong; ZHANG Qing; LIU YanGang


    The mono-protonated and di-protonated forms of copper phthalocyanine (CuPc) were obtained by increasing concentrations of trifluoroacetic acid (TFA) solution to a fixed concentration of CuPc solutions.UV-Vis spectrum shows that the Q bands of these two derivatives split and shift to the red,which means successive protonation happened and caused the two derivatives to lose their symmetry.After the protonation step,the solubility of protonated CuPc in organic solvent increased 60 times.The CuPc film was fabricated by the electrophoretic deposition (EPD) method from the protonated CuPc dissolved in nitromethane containing TFA.Scanning electron microscopy (SEM) showed that the deposited CuPc film on the indium tin oxide (ITO) substrate is composed of thread-like nanobelts with diameters between 100 nm and 200 nm.Furthermore,the CuPc film is in α phase with stacking direction (b-axis) parallel to the substrate,which was detected by X-ray diffraction.

  9. Synthesis, characterization, Hirshfeld surface analysis and antioxidant activity of a novel organic-inorganic hybrid material 1-methylpiperazine-1,4-diium bis(nitrate)

    Gatfaoui, Sofian; Mezni, Ali; Roisnel, Thierry; Marouani, Houda


    The new inorganic-organic hybrid material 1-methylpiperazine-1,4-diium bis(nitrate) (MPN) have been synthesized and crystallized to the orthorhombic system with space group Pnma and the lattice parameters obtained are a = 10.9385(9) Å, b = 6.5698 Å (4), c = 13.7021(10) Å, V = 984.68(12) Å3 and Z = 4. The trigonal (NO3-) anions are connected to the 1-methylpiperazine-1,4-diium cations via a large number of bifurcated and non-bifurcated Nsbnd H⋯O and Csbnd H⋯O hydrogen bonds. The diprotonated piperazine ring adopts a chair conformation, with the methyl group occupying an equatorial position. Intermolecular interactions in the crystal structure were quantified by Hirshfeld surface analysis. Infrared spectrum confirms the existence of the functional groups in the elaborated material. Optical absorption reveals an important band gap energy indicating stability of the title compound. The DTA/TGA and DSC curves indicate that the crystal is thermally stable up to 180 °C. The antioxidant properties were determined via the DPPH radical scavenging, the ABTS radical scavenging, hydroxyl radical scavenging and ferric reducing power (FRP).

  10. On the mechanism of chloroquine resistance in Plasmodium falciparum.

    Chinappi, Mauro


    Resistance to chloroquine of malaria strains is known to be associated with a parasite protein named PfCRT, the mutated form of which is able to reduce chloroquine accumulation in the digestive vacuole of the pathogen. Whether the protein mediates extrusion of the drug acting as a channel or as a carrier and which is the protonation state of its chloroquine substrate is the subject of a scientific debate. We present here an analytical approach that explores which combination of hypotheses on the mechanism of transport and the protonation state of chloroquine are consistent with available equilibrium experimental data. We show that the available experimental data are not, by themselves, sufficient to conclude whether the protein acts as a channel or as a transporter, which explains the origin of their different interpretation by different authors. Interestingly, though, each of the two models is only consistent with a subset of hypotheses on the protonation state of the transported molecule. The combination of these results with a sequence and structure analysis of PfCRT, which strongly suggests that the molecule is a carrier, indicates that the transported species is either or both the mono and di-protonated forms of chloroquine. We believe that our results, besides shedding light on the mechanism of chloroquine resistance in P. falciparum, have implications for the development of novel therapies against resistant malaria strains and demonstrate the usefulness of an approach combining systems biology strategies with structural bioinformatics and experimental data.

  11. Interactions of squaric acid with DABCO mono-betaine: Structural, spectroscopic and calculation studies

    Barczyński, P.; Dega-Szafran, Z.; Katrusiak, A.; Szafran, M.


    The 1:1 complex of squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dion) with DABCO mono-betaine (1-carboxymethyl-1,4-diazabicyclo[2.2.2]octane inner salt), 1, has been characterized by single-crystal X-ray analysis, FTIR and NMR spectroscopies and by DFT calculations. The crystal of 1 is triclinic, space group P1¯. Short COOH⋯O and Nsbnd H⋯O hydrogen bonds of 2.445(2) and 2.582(2) Å, respectively, link the diprotonated DABCO mono-betaine dications and squarate dianions into chain. The structure is additionally stabilized by the N+⋯O electrostatic interactions and weak Csbnd H⋯O hydrogen bonds. The FTIR spectrum shows two broad absorptions in the 3000-2000 cm-1 region assigned to the νNsbnd H⋯O vibration and in the 1900-500 cm-1 region attributed to the ν(OHO) and γ(OHO) vibrations of the short hydrogen bonds.

  12. Zirconium and Titanium Propylene Polymerization Precatalysts Supported by a Fluxional C 2 -Symmetric Bis(anilide)pyridine Ligand

    Tonks, Ian A.


    Titanium and zirconium complexes supported by a bis(anilide)pyridine ligand (NNN = pyridine-2,6-bis(N-mesitylanilide)) have been synthesized and crystallographically characterized. C 2-symmetric bis(dimethylamide) complexes were generated from aminolysis of M(NMe 2) 4 with the neutral, diprotonated NNN ligand or by salt metathesis of the dipotassium salt of NNN with M(NMe 2) 2Cl 2. In contrast to the case for previously reported pyridine bis(phenoxide) complexes, the ligand geometry of these complexes appears to be dictated by chelate ring strain rather than metal-ligand π bonding. The crystal structures of the five-coordinate dihalide complexes (NNN)MCl 2 (M = Ti, Zr) display a C 1-symmetric geometry with a stabilizing ipso interaction between the metal and the anilido ligand. Coordination of THF to (NNN)ZrCl 2 generates a six-coordinate C 2-symmetric complex. Facile antipode interconversion of the C 2 complexes, possibly via flat C 2v intermediates, has been investigated by variable-temperature 1H NMR spectroscopy for (NNN)MX 2(THF) n (M = Ti, Zr; X = NMe 2, Cl) and (NNN)Zr(CH 2Ph) 2. These complexes were tested as propylene polymerization precatalysts, with most complexes giving low to moderate activities (10 2-10 4 g/(mol h)) for the formation of stereoirregular polypropylene. © 2012 American Chemical Society.

  13. Tris(ethylenediammonium bis[(2-aminoethylammonium] bis[bis(μ5-hydrogen phosphatopenta-μ2-oxido-decaoxidopentamolybdenum(VI] decahydrate

    Jing Lu


    Full Text Available The title compound, (C2H10N23(C2H9N22[Mo5(HPO42O15]·10H2O, was prepared under hydrothermal conditions at pH 5.0. The structure contains mono- and diprotonated ethylenediamine cations, [Mo5O15(HPO42]4− anions and uncoordinated water molecules. The [Mo5O15(HPO42]4− heteropolyoxometallate anion is made up of five MoO6 octahedra sharing an edge and forming a ring, which is closed by common corners of the terminal MoO6 octahedron. The ring is topped on both sides by two slightly distorted PO4 tetrahedra, sharing three corners with three MoO6 octahedra. The terminal oxygen atoms of the PO4 units are protonated. Together with the anions, the water molecules and the ethylenediammonium cations are involved in N—H...O and O—H...O hydrogen bonding, forming a three-dimensional supramolecular network.

  14. Study on the supramolecular system of meso-tetrakis (4-sulfonatophenyl) porphyrin and cyclodextrins by spectroscopy

    Wang, Xiao-ping; Pan, Jing-hao; Shuang, Shao-min


    The ability of β-cyclodextrin (β-CD), sulfurbutylether-β-CD (SBE-β-CD) and hydroxypropyl-β-CD (HP-β-CD) to break the aggregate of the meso-Tetrakis (4-sulfonatophenyl) porphyrin (TPPS 4) and to form 2:1 inclusion complexes has been studied by adsorption and fluorescence spectroscopy. The formation constants are calculated, respectively by fluoremetry, from which the inclusion capacity of different CDs is compared and the inclusion mechanism of charged-β-CD (SBE-β-CD) is quite different from that of parent β-CD. At lower pH, the complexation between HP-β-CD and H 2TPPS 42+ (the form of the diprotonated TPPS 4) hampers the continuous protonation of the pyrrole nitrogen of TPPS 4 and the hydrophobic cavity may prefer to bind an apolar neutral porphyrin molecule. 1HNMR data support the inclusion conformation of the porphyrin-cyclodextrin supramolecular system, indicating the interaction of meso-phenyl groups of TPPS 4 with the cavity of CDs. For this host-guest inclusion model, cyclodextrin, being regarded as the protein component, which acts as a carrier enveloping the active site of heme prosthetic group within its hydrophobic environment, provides a protective sheath for porphyrin, creating artificial analogues of heme-containing proteins. However, the TPPS 4, encapsulated within this saccharide-coated barrier, its physico-chemical, photophysical and photochemical properties changed strongly.

  15. 1-[Bis(4-fluorophenylmethyl]-4-[(2Z-3-phenylprop-2-en-1-yl]piperazine-1,4-diium dichloride hemihydrate

    S. Shivaprakash


    Full Text Available The asymmetric unit of the title monohydrated salt, 2C26H28F2N22+·4Cl−.H2O, consists of a 1-[bis(4-fluorophenylmethyl]-4-[(2Z-3-phenylprop-2-en-1-yl]piperazine-1,4-diium cation with a diprotonated piperizine ring in close proximity to two chloride anions and a single water molecule that lies on a twofold rotation axis. In the cation, the piperazine ring adopts a slightly distorted chair conformation. The dihedral angles between the phenyl ring and the 4-fluorophenyl rings are 89.3 (9 and 35.0 (5°. The two fluorophenyl rings are inclined at 65.0 (5° to one another. In the crystal, N—H...Cl hydrogen bonds and weak C—H...Cl intermolecular interactions link the molecules into chains along [010]. In addition, weak C—H...O interactions between the piperizine and prop-2-en-1-yl groups with the water molecule, along with weak C—H...Cl interactions between the prop-2en-1-yl and methyl groups with the chloride ions, weak C—H...F interactions between the two fluorophenyl groups and weak O—H...Cl interactions between the water molecule and chloride ions form a three-dimensional supramolecular network.

  16. Shape-persistent macrocycles functionalised with coumarin dyes: acid-controlled energy- and electron-transfer processes.

    Giansante, Carlo; Ceroni, Paola; Venturi, Margherita; Balzani, Vincenzo; Sakamoto, Junji; Schlüter, A Dieter


    We have investigated the spectroscopic properties (absorption spectra, emission spectra, emission lifetimes) of three triads in CH(2)Cl(2): C2-M-C2, C343-M-C343, and C2-M-C343, in which M is a shape-persistent macrocyclic hexagonal backbone composed of two 2,2'-bipyridine (bpy) units embedded in opposing sides, and C2 and C343 are coumarin 2 and coumarin 343, respectively. All the components are strongly fluorescent species (Phi=0.90, 0.79, and 0.93 for M, C2, and C343, respectively, as established by investigating suitable model compounds). In each triad excitation of M leads to almost quantitative energy transfer to the lowest coumarin-localised excited state. Upon addition of acid, the two bpy units of the M component undergo independent protonation leading to monoprotonated (e.g., C2-MH(+)-C2) and diprotonated (e.g., C2-M2 H(+)-C2) species. Further addition of acid leads to protonation of the coumarin component so that each triad is involved in four protonation equilibria. Protonation causes strong (and reversible, upon addition of base) changes in the absorption and fluorescence properties of the triads because of inversion of the excited-state order and/or the occurrence of electron-transfer quenching processes.

  17. Structures of Annulenes and Model Annulene Systems in the Ground and Lowest Excited States

    Pier Remigio Salvi


    Full Text Available The paper introduces general considerations on structural properties of aromatic, antiaromatic and non-aromatic conjugated systems in terms of potential energy along bond length alternation and distortion coordinates, taking as examples benzene, cyclobutadiene and cyclooctatetraene. Pentalene, formally derived from cyclooctatetraene by cross linking, is also considered as a typical antiaromatic system. The main interest is concerned with [n]annulenes and model [n]annulene molecular systems, n ranging from 10 to 18. The rich variety of conformational and  configurational isomers and of dynamical processes among them is described. Specific attention is devoted to bridged [10]- and [14]annulenes in the ground and lowest excited states as well as to s-indacene and biphenylene. Experimental data obtained from vibrational and electronic spectroscopies are discussed and compared with ab initio calculation results. Finally, porphyrin, tetraoxaporphyrin dication and diprotonated porphyrin are presented as annulene structures adopting planar/non-planar geometries depending on the steric hindrance in the inner macrocycle ring. Radiative and non-radiative relaxation processes from excited state levels have been observed by means of time-resolved fluorescence and femtosecond transient absorption spectroscopy. A short account is also given of porphycene, the structural isomer of porphyrin, and of porphycene properties.

  18. A New Organo-templated Layered Zincophosphate Synthesized from a Solvothermal System Containing Racemic1,2-Diaminopropane


    A new layered zincophosphate was synthesized under solvothermal conditions by employing racemic 1,2-diaminopropane as the structure-directing agent. The structure of the compound was solved by means of single-crystal X-ray diffraction analysis. It crystallized in the monoclinic space group P21/c (No. 14) with a=1.047 0(3) nm, b=0.787 31(18) nm, c=0.662 68(16) nm, β=103.120(5)°, V=0.532 0(2) nm3 and Z=4. The structure is made up of anionic zincophosphate sheets stacked in an AAAA sequence. The individual sheet contains three- and four-membered rings and the infinite Zn-O-Zn chains can also be envisaged in the sheet. The charge-balancing diprotonated racemic 1,2-diaminopropane cations are sandwiched between the layers, whereas the inorganic layers are stabilized by strong H-bonds formed between the N atoms of the amine and the O atoms in the inorganic sheets.

  19. Crystal structures of salts of mono- and triprotonated [3(6)]adamanzane, 1,5,9,13-tetraazatricyclo[,13)]docosane, and equilibrium studies of the reactions between mono-, di- and triprotonated species, respectively, having none, one and two lone pairs pointing outwards

    Springborg, Johan; Pretzmann, Ulla; Olsen, Carl Erik;


    The structures of bromide salt of the inside monoprotonated tricyclic amine 1,5,9,13-tetraazatricyclo[,13)]docosane, i(+),i,i,i-[H[3(6)]adz]Br and of the tetrabromozincate bromide salt of its triprotonated form, i(+),i,o(+),o(+)-[H-3[3(6)]adz][ZnBr(4)lBr-H2O have been determined by X......-ray diffraction techniques. In acidic solution i(+),i,i,i-H[3(6)]adz(+) reacts with one hydrogen ion and at the same time undergoes inversion at one nitrogen group to give the diprotonated species i(+),i,i,o(+)-H-2[3(6)]adz(2+) as shown by H-1 and C-13 NMR spectroscopy and glass-electrode measurements...... a time-averaged T-d symmetry. The latter is interpreted as a fast exchange of the outside coordinated proton between the four sites in i(+),i,i,o(+)-H-2[3(6)]adz(2+). The exchange reaction is acid catalyzed, and a pathway involving the triprotonated species i(+),i,o(+),o(+) -H-3[3(6)]adz(3+) is assumed...

  20. Synthesis, Characterization and Crystal Structure of an Inorganic-organic Composite Metatungstate: [Co(4,4'-bipy)2(H2O)4](4,4'-H2bipy)2[H2W12O40]·5.5H2O


    A novel hybrid compound [Co(4,4'-bipy)2(H2O)4](4,4'- H2bipy)2[H2W12O40]·5.5H2Ohas been synthesized from an acidified aqueous solution and characterized by elemental and thermal analyses, IR and UV spectroscopy, and single-crystal X-ray structure determination. Structure analysis indicates that the title compound is of monoclinic, space group C2/c, with a = 21.315(9), b = 15.303 (7), c = 24.139(10) (A), β = 105.170(5)o, V = 7599(6) (A)3, Mr = 3706.99, Z = 4, F(000) = 6616, Dc = 3.231, μ = 18.395 mm-1, R = 0.0652 and wR = 0.1594. X-ray crystallographic study shows that the title compound consists of one [Co(4,4'-bipy)2(H2O)4]2+ cation, two diprotonated 4,4'-bipyridine molecules, 5.5 water molecules of crystallization, and one metatungstate polyoxoanion [H2W12O40]6-, which approaches an effective Td point symmetry. TG-DTA analysis indicates that the framework of the metatungstate polyoxoanion is collapsed at 587.0 ℃.

  1. Cucurbit[7]uril host-guest complexes of the histamine H2-receptor antagonist ranitidine.

    Wang, Ruibing; Macartney, Donal H


    The macrocyclic host cucurbit[7]uril forms very stable complexes with the diprotonated (K(CB[7])(1) = 1.8 x 10(8) dm(3) mol(-1)), monoprotonated (K(CB[7])(2) = 1.0 x 10(7) dm(3) mol(-1)), and neutral (K(CB[7])(3) = 1.2 x 10(3) dm(3) mol(-1)) forms of the histamine H(2)-receptor antagonist ranitidine in aqueous solution. The complexation behaviour was investigated using (1)H NMR and UV-visible spectroscopy as a function of pH and the pK(a) values of the guest were observed to increase (DeltapK(a1) = 1.5 and DeltapK(a2) = 1.6) upon host-guest complex formation. The energy-minimized structures of the host-guest complexes with the cationic guests were determined and provide agreement with the NMR results indicating the location of the CB[7] over the central portion of the guest. The inclusion of the monoprotonated form of ranitidine slows the normally rapid (E)-(Z) exchange process and generates a preference for the (Z) isomer. The formation of the CB[7] host-guest complex greatly increases the thermal stability of ranitidine in acidic aqueous solution at 50 degrees C, but has no effect on its photochemical reactivity.

  2. Guest-directed supramolecular architectures of {W36} polyoxometalate crowns.

    McGlone, Thomas; Streb, Carsten; Long, De-Liang; Cronin, Leroy


    The {W36} isopolyoxotungstate cluster provides a stable inorganic molecular platform for the binding of inorganic and organic guest molecules. This is achieved by a binding pocket formed by six terminal oxo ligands located in the central cavity of the all-inorganic cation binding host. Previously it was shown that the cluster can specifically bind primary amines and importantly, functionalized diamines through a combination of electrostatic and hydrogen bonding interactions. Here we transform this assembly strategy to utilize the binding of long-chain alkyldiammonium guest cations to physically define the supramolecular structure of the clusters with respect to each other and demonstrate the structure direction as a function of alkyl chain length. The systematic variation of the chain length gives access to five supramolecular assemblies which were all fully characterized using single crystal XRD, TGA, 1H NMR, and elemental analysis. In compound 1, diprotonated 1,8-diaminooctane molecules link the {W36} clusters into infinite 1D zigzag chains, whereas compounds 2 and 3 feature trimeric {W36} assemblies directly connected through protonated 1,9-diaminononane (2) or 1,10-diaminodecane (3) linkers. Compound 4 contains dumb-bell shaped dimeric units as a result of direct center-to-center linkages between the {W36} clusters formed by protonated 1,12-diaminododecane. In compound 5, triply protonated bis(hexamethylene)triamine was employed to obtain linear 1D chains of directly connected {W36} cluster units.

  3. Studies on Synthetic and Natural Melanin and Its Affinity for Fe(III Ion

    T. G. Costa


    Full Text Available In this work, we measured the metal-binding sites of natural and synthetic dihydroxyindole (DHI melanins and their respective interactions with Fe(III ions. Besides the two acid groups detected for the DHI system: catechol (Cat and quinone-imine (QI, acetate groups were detected in the natural oligomer by potentiometric titrations. At acidic pH values, Fe(III complexation with synthetic melanin was detected in an Fe(OH(CatH2Cat interaction. With an increase of pH, three new interactions occurred: dihydroxide diprotonated catechol, Fe(OH2(CatH2Cat−, dihydroxide monoprotonated catechol, [Fe(OH2(CatHCat]2−, and an interaction resulting from the association of one quinone-imine and a catechol group, [Fe(OH2(Qi−(CatHCat]3−. In the natural melanin system, we detected the same interactions involving catechol and quinone-imine groups but also the metal interacts with acetate group at pH values lower than 4.0. Furthermore, interactions in the synthetic system were also characterized by infrared spectroscopy by using the characteristic vibrations of catechol and quinone-imine groups. Finally, scanning electronic microscopy (SEM and energy-dispersive X-ray (EDS analysis were used to examine the differences in morphology of these two systems in the absence and presence of Fe(III ions. The mole ratio of metal and donor atoms was obtained by the EDS analysis.

  4. X-ray and Synchrotron Diffraction Studies of 2-(Pyridin-2-yl)-1,10- Phenanthroline in the Role of Ligand for Two Copper Polymorphs or Hydrogen bonded with 2,2,6,6-Tetramethyl-4-oxopiperidinium Hexafluorophosphate

    Krause, Jeanette A.; Zhao, Daoli; Chatterjee, Sayandev; Yeung, Bonnie M.; Connick, William B.; Collins, Sibrina N.


    Different extended packing motifs of dichloro-[2-(pyridin-2-yl)-1,10-phenanthroline]copper(II), CuCl2 (C17H11N3Cl2) are obtained depending on the crystallization conditions. A triclinic form (I) is obtained from dimethylformamide-diethyl ether or methanol whereas crystallization from dimethylformamide-water yields a monoclinic form (II). In each case, the CuII center is in a 5-coordinate, distorted square-pyramidal geometry. The extended packing for both forms can be described as a highly-offset π stacking arrangement with interlayer distances of 3.674 (3) and 3.679 (3) Å for (I) and (II), respectively. The reaction of diprotonated Pt(tmpip2NCN)Cl (tmpip2NCN = 2,6-bis(2,2,6,6-tetramethylpiperidylmethyl)- benzyl) with AgPF6 under acidic conditions followed by the addition of 2-(pyridin-2-yl)-1,10-phenanthroline, results in a hydrogen bonded co-crystal, 2,2,6,6-tetramethyl-4-oxopiperidinium hexafluorophosphate- 2-(pyridin-2-yl)-1,10-phenanthroline (1/1),C9H18NO+.PF6-.C17H11N3.(III). The extended packing maximizes π-π interactions in a parallel, faceto-face arrangement with an interlayer stacking distance of 3.4960 (14) Å.

  5. Three-body model for the two-neutron decay of $^{16}$Be

    Lovell, A E; Thompson, I J


    While diproton decay was first theorized in 1960 and first measured in 2002, it was first observed only in 2012. The measurement of $^{14}$Be in coincidence with two neutrons suggests that $^{16}$Be does decay through the simultaneous emission of two strongly correlated neutrons. In this work, we construct a full three-body model of $^{16}$Be (as $^{14}$Be + n + n) in order to investigate its configuration in the continuum and in particular the structure of its ground state. In order to describe the three-body system, effective n-$^{14}$Be potentials were constructed, constrained by the experimental information on $^{15}$Be. The hyperspherical R-matrix method was used to solve the three-body scattering problem, and the resonance energy of $^{16}$Be was extracted from a phase shift analysis. In order to reproduce the experimental resonance energy of $^{16}$Be within this three-body model, a three-body interaction was needed. For extracting the width of the ground state of $^{16}$Be, we use the full width at ha...

  6. Potentiometric response and mechanism of anionic recognition of heterocalixarene-based ion selective electrodes

    Shishkanova, T.V. [Department of Analytical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)]. E-mail:; Sykora, D. [Department of Analytical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); Sessler, J.L. [Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, University of Texas, Austin, TX 78712-0615 (United States); Kral, V. [Department of Analytical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)


    The ion selective electrode (ISE)-based potentiometric approach is shown to be an effective means of characterizing the anion recognition sites in the molecular receptor calix[2]pyridino[2]pyrrole (CPP). In particular, potentiometric pH-measurements involving the use of experimental PVC-membranes based on CPP revealed the existence of both mono- and diprotonated forms of the receptor under readily accessible conditions. Based on these analyses, apparent surface protonation constants for this heterocalixarene were found to lie between 8.5-8.9 (pK {sub B1}) and 3.3-3.8 (pK {sub B2}). CPP was found to interact with targeted anionic analytes based on both coulombic and hydrogen bond interactions, as inferred from varying the kinds of ionic sites present within the membrane phase. Potentiometric selectivity studies revealed that CPP preferred 'Y-shaped' anions (e.g. acetate, lactate, benzoate) over spherical anions (e.g. fluoride and chloride), fluoride over chloride within the set of spherical anions, and the ortho-isomer over the corresponding meta- and para-isomers in the case of hydroxybenzoate (salicylate and congeners). In the context of this study, the advantages of potentiometric determinations of acetylsalicylic acid using optimized PVC-membranes based on CPP relative to more conventional PVC-membrane ISEs based on traditional anion exchanger were also demonstrated.

  7. Synthesis, crystal structure, and protonation behaviour in solution of the recently-discovered drug metabolite, N1,N10-diacetyltriethylenetetramine

    Wichmann, Kathrin A.; Söhnel, Tilo; Cooper, Garth J. S.


    N1,N10-diacetyltriethylenetetramine (DAT) is a recently-discovered major in vivo metabolite of triethylenetetramine (TETA), a highly-selective CuII chelator currently under clinical development as a novel first-in-class therapeutic for the cardiovascular, renal and retinal complications of diabetes mellitus. Characterisation of DAT is an integral aspect of the pharmacological work-up required to support this clinical development programme and, to our knowledge, no previous synthesis for it has been published. Here we report the synthesis of DAT dihydrochloride (DAT·2 HCl); its crystal structure as determined by X-ray single-crystal (XRD) and powder diffraction (XRPD); and protonation constants and species distribution in aqueous solution, which represents the different protonation states of DAT at different pH values. The crystal structure of DAT·2 HCl reveals 3D-assemblies of alternating 2D-layers comprising di-protonated DAT strands and anionic species, which form an extensive hydrogen-bond network between amine groups, acetyl groups, and chloride anions. Potentiometric titrations show that HDAT+ is the physiologically relevant state of DAT in solution. These findings contribute to the understanding of TETA's pharmacology and to its development for the experimental therapeutics of the diabetic complications.

  8. Dual effect of local anesthetics on the function of excitable rod outer segment disk membrane

    Mashimo, T.; Abe, K.; Yoshiya, I.


    The effects of local anesthetics and a divalent cation, Ca2+, on the function of rhodopsin were estimated from the measurements of light-induced proton uptake. The light-induced proton uptake by rhodopsin in the rod outer segment disk membrane was enhanced at lower pH (4) but depressed at higher pHs (6 to 8) by the tertiary amine local anesthetics lidocaine, bupivacaine, tetracaine, and dibucaine. The order of local anesthetic-induced depression of the proton uptake followed that of their clinical anesthetic potencies. The depression of the proton uptake versus the concentration of the uncharged form of local anesthetic nearly describes the same curve for small and large dose of added anesthetic. Furthermore, a neutral local anesthetic, benzocaine, depressed the proton uptake at all pHs between 4 and 7. These results indicate that the depression of the proton uptake is due to the effect of only the uncharged form. It is hypothesized that the uncharged form of local anesthetics interacts hydrophobically with the rhodopsin in the disk membrane. The dual effect of local anesthetics on the proton uptake, on the other hand, suggests that the activation of the function of rhodopsin may be caused by the charged form. There was no significant change in the light-induced proton uptake by rhodopsin when 1 mM of Ca2+ was introduced into the disk membrane at varying pHs in the absence or presence of local anesthetics. This fact indicates that Ca2+ ion does not influence the diprotonating process of metarhodopsin; neither does it interfere with the local anesthetic-induced changes in the rhodopsin molecule.

  9. A realtime, online automated system for measurement of Phosphate ions in atmospheric particles

    Violaki, Kalliopi; Fang, Ting; Mihalopoulos, Nikos; Weber, Rodney James; Nenes, Athanasios


    Primary productivity of continental and marine ecosystems is often limited or co-limited by phosphorus. Of particular interest is the role of phosphorus in marine primary productivity, owing to its potential for affecting the concentration of atmospheric carbon dioxide. The atmosphere is considered a principal source of externally-supplied nutrients for large areas of the surface ocean, and oligotrophic open oceans in particular. Atmospheric inorganic P species (e.g. mono- or diprotonated orthophosphate) comprise the most bioavailable P form, and have been studied for many decades. Nevertheless, there are very large uncertainties in the phosphate biogeochemical budget due to the lack of observations and the poor match of the model to observations. This study presents a novel automated on-line, real-time analytical method for the analysis of water-soluble PO4-3 ions in atmospheric particles. The instrumentation consists of a particle-into-liquid sampler (PILS) coupled with a reaction coil to allow reagents to interact with the PILS liquid flow; the composite flow is then introduced into a mini spectrophotometer, which is equipped with a long path length of 250cm Liquid Wavequide Capillary Cell (LWCC), achieving low detection limit. This new system overcomes the limitations on detection and time resolution, as the configuration presented allows for measurement with 8 minute resolution. The data, when combined with routine PILS-IC or aerosol mass spectrometry, allows for an unprecedented insight towards the drivers of phosphate solubility and its relation to acidification from atmospheric acids. We present results for concentration of PM2.5 PO4-3 in Atlanta Georgia for a 2 month period (February-March, 2015) and the Eastern Mediterranean and its relation to aerosol acidity and other meteorological parameters. The results are discussed together with future directions towards optimized performance during long periods of operation.

  10. Proton and Two-proton Emissions from Proton-rich Nuclei with 10 6 Z 6 20

    林承键; 金仕纶; 黄美容; 白真; 吴振东; 杨峰; 胡正国; 王猛; 雷相国; 张焕乔; 徐瑚珊; 徐新星; 肖国青; 王建松; 孙立杰; 贾会明; 杨磊; 马朋; 马军兵; 杨彦云


    Proton (p) and two-proton (2p) emissions from the proton-rich nuclei with 10 6 Z 6 20 have been explored by the in-fight decay and implantation decay methods, respectively, in a series of experi-ments at the HIRFL-RIBLL facility. The in-flight 2p emissions from the excited states of 28,29S/26,27P and 17,18Ne were studied by complete-kinematics measurements. Mechanisms of 2p decay and related p-p correlations have been explored. Obvious 2p correlated emissions have been observed in the cases of 28,29S but not in 27,28P, indicating the 2p halo plays an important role in the diproton emission. In the 17,18Ne cases, a small 2p opening angles were deduced by the HBT analyses, implying the BCS-BEC crossover may occur in the dilute nuclear matter. Moreover, 27S/26P/25Si, 22Si/20Mg, 23Si/22Al/21Mg, 24Si/23Al, and 36,37Ca were implanted in a thin double-sided-silicon-strip detector and their β-delayed p and 2p decays have been measured by a surrounding silicon detector array under the continuous-beam mode. Important information on the nuclear spectroscopy, such as energy, lifetime, branching-ratio, and so on, has been extracted, which helps us to understand the nuclear structures of proton-rich exotic nuclei close to the drip-line.

  11. Separation of lanthanides and actinides(III) using tridentate benzimidazole, benzoxazole and benzothiazole ligands

    Drew, M.G.B.; Hudson, M.J.; Iveson, P.B.; Vaillant, L.; Youngs, T.G.A. [Reading Univ. (United Kingdom). Dept. of Chemistry; Hill, C.; Madic, Ch. [CEA Valrho, Dir. de l' Energie Nucleaire, Departement RadioChimie et Procedes, Service de Chimie des Procedes de Separation (DEN/DRCP/SCPS/LCSE), 30 - Marcoule (France)


    The ability of new hydrophobic tridentate ligands based on 2,6-bis(benzimidazole-2-yl)pyridine, 2,6-bis(benzoxazole-2-yl)pyridine and 2,6-bis(benzothiazole-2-yl)pyridine to selectively extract americium(III) from europium(III) was measured. The most promising ligand - 2,6-bis(benzoxazole-2-yl)-4-(2-decyl-1-tetra-decyl-oxy)pyridine L{sup 9} was found to give separation factors (SF{sub Am/Eu}) of up to 70 when used to extract cations from 0.02-0.10 M HNO{sub 3} into TPH in synergy with 2-bromo-decanoic acid. Six structures of lanthanide complexes with 2,6-bis(benzoxazole-2-yl)pyridine L{sup 6} were then determined to evaluate the types of species that are likely to be involved in the separation process. Three structural types were observed, namely [LnL{sup 6}(NO{sub 3}){sub 3}(H{sub 2}O){sub 2}), 11-coordinate only for La, [LnL{sup 6}(NO{sub 3})3 (CH{sub 3}CN)], 10-coordinate for Pr, Nd and Eu and [LnL{sup 6}(NO{sub 3}){sub 3}(H{sub 2}O)], L 10-coordinate for Eu and Gd. Quantum Mechanics calculations were carried out on the tridentate ligands to elucidate the conformational preferences of the ligands in the free state and protonated and di-protonated forms and to assess the electronic properties of the ligands for comparison with other ter-dentate ligands used in lanthanide/actinide separation processes. (authors)

  12. Spectroelectrochemical and computational studies on the mechanism of hypoxia selectivity of copper radiopharmaceuticals.

    Holland, Jason P; Barnard, Peter J; Collison, David; Dilworth, Jonathan R; Edge, Ruth; Green, Jennifer C; McInnes, Eric J L


    Detailed chemical, spectroelectrochemical and computational studies have been used to investigate the mechanism of hypoxia selectivity of a range of copper radiopharmaceuticals. A revised mechanism involving a delicate balance between cellular uptake, intracellular reduction, reoxidation, protonation and ligand dissociation is proposed. This mechanism accounts for observed differences in the reported cellular uptake and washout of related copper bis(thiosemicarbazonato) complexes. Three copper and zinc complexes have been characterised by X-ray crystallography and the redox chemistry of a series of copper complexes has been investigated by using electronic absorption and EPR spectroelectrochemistry. Time-dependent density functional theory (TD-DFT) calculations have also been used to probe the electronic structures of intermediate species and assign the electronic absorption spectra. DFT calculations also show that one-electron oxidation is ligand-based, leading to the formation of cationic triplet species. In the absence of protons, metal-centred one-electron reduction gives the reduced anionic copper(I) species, [CuIATSM](-), and for the first time it is shown that molecular oxygen can reoxidise this anion to give the neutral, lipophilic parent complexes, which can wash out of cells. The electrochemistry is pH dependent and in the presence of stronger acids both chemical and electrochemical reduction leads to quantitative and rapid dissociation of copper(I) ions from the mono- or diprotonated complexes, [CuIATSMH] and [Cu(I)ATSMH2]+. In addition, a range of protonated intermediate species have been identified at lower acid concentrations. The one-electron reduction potential, rate of reoxidation of the copper(I) anionic species and ease of protonation are dependent on the structure of the ligand, which also governs their observed behaviour in vivo.

  13. The hydrolysis kinetics of monobasic and dibasic aminoalkyl esters of ketorolac.

    Qandil, Amjad M; Jamhawi, Noor M; Tashtoush, Bassam M; Al-Ajlouni, Ahmad M; Idkaidek, Nasir M; Obaidat, Aiman A


    Six aminoethyl and aminobutyl esters of ketorolac containing 1-methylpiperazine (MPE and MPB), N-acetylpiperazine (APE and APB) or morpholine (ME and MB), were synthesized and their hydrolysis kinetics were studied. The hydrolysis was studied at pH 1 to 9 (for MPE, APE and ME) and pH 1 to 8 (for MPB, APB and MB) in aqueous phosphate buffer (0.16 M) with ionic strength (0.5 M) at 37°C. Calculation of k(obs), construction of the pH-rate profiles and determination of the rate equations were performed using KaleidaGraph® 4.1. The hydrolysis displays pseudo-first order kinetics and the pH-rate profiles shows that the aminobutyl esters, MPE, APB and MB, are the most stable. The hydrolysis of the ethyl esters MPE, APE and ME, depending on the pH, is either fast and catalyzed by the hydroxide anion or slow and uncatalyzed for the diprotonated, monoprotonated and nonprotonated forms. The hydrolysis of the butyl esters showed a similar profile, albeit it was also catalyzed by hydronium cation. In addition, the hydroxide anion is 105 more effective in catalyzing the hydrolysis than the hydronium cation. The hydrolysis pattern of the aminoethyl esters is affected by the number and pKa of its basic nitrogen atoms. The monobasic APE and ME, show a similar hydrolysis pattern that is different than the dibasic MPE. The length of the side chain and the pKa of the basic nitrogen atoms in the aminoethyl moiety affect the mechanism of hydrolysis as the extent of protonation at a given pH is directly related to the pKa.

  14. Potentiometric investigation of acid-base equilibria of two newv pyrimidine derivatives in various methanol–water media



    Full Text Available The acid-base properties of 1-amino-5-benzoyl-4-phenyl-1H-pyrimidine-2-one (L1 and 1-amino-5-benzoyl-4-phenyl-1H-pyrimidine-2-thione (L2 were investigated potentiometrically at an ionic strength of 0.10M(LiCl in 19.8, 33.6 and 55.9 % (v/v methanol–water mixtures at 25.0 ± 0.1 ºC. The apparent dissociation constants (psKa were calculated for the di-protonated form (L1H2+2 and L2H2+2 of pyrimidine bases, using a software package TITFIT, which were then extrapolated to pure water to derive the dissociation constants in aqueous solution (pKa. The aqueous pKa constants were found to be: L1, pKa1 = 3.76 and pKa2 = 6.95; L2, pKa1 = 3.57 and pKa1 = 6.90. At pH 2.00, the dominant species in solution were the protonated form of the amino group substituted at the 1-position, while at a pH around 5.00, they were the protonated form of the pyrimidine ring nitrogen at the 3-position. An effect of intramolecular hydrogen bonding on the psKa values was observed with L1 but not L2. The effects ofmolecular structure and solvent medium on the psKa values are also discussed.

  15. What can quantum chemistry tell us about Pa(V) hydration and hydrolysis?

    Siboulet, B. [CEA Marcoule, Lab. de Conception des Architectures Moleculaires (DRCP/SCPS), 30 (France); Marsden, C.J. [Universite P. Sabatier, Lab. de Physique Quantique, CNRS-UMR 5626, 31 - Toulouse (France); Vitorge, P. [CEA Saclay, Lab. de Speciation des Radionucleides et Molecules (UMR 8587DPC/SECR), 91 - Gif-sur-Yvette (France)


    Published liquid-liquid extraction studies of Pa(V) were interpreted with aqueous mono-, di- and tri cations. B3LYP DFT is applied here to such cations surrounded by two explicit hydration layers: Linear or tetrahedral geometries are found for the Pa(V) aquo ions. PaO{sub 2}{sup +} is similar to the other AnO{sub 2}{sup +} cations, but has strong apical bonds, resulting from the highly negative O{sub yl} charge, which decreases along the An(V) series. This explains the instability of PaO{sub 2}{sup +} in water, and the differences with the heavier An(V). PaO{sub 2}{sup +} di-protonates to give Pa(OH){sub 2}{sup 3+} and can further di-hydrolyze to give T{sub d}-Pa(OH){sub 4}{sup +}, which might very well be the most stable Pa(V) mono cation. PaOOH{sup 2+} is confirmed to be the Pa(V) aqueous di cation invoked in the literature for pH{<=} 1.4 {+-} 0.7. PaO{sup 3+} is confirmed in sulfate solution, with a bond length close to 180 pm. Pa(OH){sub 2}{sup 3+} cannot be excluded in other conditions. The strong influence of the solvent was not fully taken into account in most previous theoretical studies that focused only on bare or partially solvated PaO{sub 2}{sup +}. Toraishi et al. have studied hydrated Pa(V) and our work confirms this study and its qualitative interpretation. The new tetrahedral Pa(OH){sub 4}{sup +} geometry that is shown here to be important opens the field to further quantum chemical studies of Pa(V) and other f-elements. As a test for the two-shell model approach for Pa(V), fluoride coordination to Pa(V) is studied and compared with published EXAFS data: an excellent fit is obtained with the well-established species PaF{sub 7}{sup 2-}, but most other stoichiometries tested are precluded. (authors)

  16. Crystalline products isolated from solutions with commercially available 2,3-bis(2-pyridyl)pyrazine (dpp) as reactant: Detection of a dimerized form of dpp

    Grove, Hilde; Frøystein, Nils Åge; Sæthre, Leif J.; Sletten, Jorunn


    From reaction mixtures of commercially available 2,3-bis(2-pyridyl)pyrazine (dpp) and perchloric acid four different solid products have been isolated and structurally characterized by X-ray crystallography; (dppH 2)(ClO 4) 2·3H 2O ( 1), (dppH 2)(ClO 4) 2 ( 2), (ddppH 2)(ClO 4) 2 ( 3) and (dppH)(ClO 4) ( 4) (dppH is monoprotonated dpp, dppH 2 is the diprotonated dication of dpp, ddppH 2 is the dication 5,5'-bis(2,3-bis(2-pyridyl)pyrazinium), i.e. dimerized dppH). In 1 and 2 the nitrogen atom in both of the pyridyl rings in dpp is protonated. Hydrogen bonding and packing arrangements differ in the two compounds. In 3 a protonated and dimerized form of dpp is found; two 2,3-bis(2-pyridyl)pyrazinium units are connected by a C(sp 2) sbnd C(sp 2) bond in the 5-positions of the pyrazine rings, one pyridyl ring in each dpp moiety being protonated at the nitrogen. Strong intra-cation N sbnd H⋯N bonds between pyridyl rings are present. In 4 the monomeric dppH moieties display the same type of intramolecular hydrogen bonds as found in 3. Upon reacting dpp with copper(II) salts and oxalate, a dinuclear copper (II) complex, [Cu 2(ddpp)(ox) 2(H 2O) 2] (ddpp = 5,5'-bis(2,3-bis(2-pyridyl)pyrazine)), as well as mononuclear [Cu(dpp)(ox)(H 2O)] have been obtained in the same reaction mixtures. In one of the isolated crystalline products a dimer of dpp is found, as described in the case of compound 3, but no protonation has occurred. The crystal structure determination reveals a dinuclear complex with the neutral ddpp (dimerized dpp) as bridging ligand. Oxalate occurs as a bidentate, terminal ligand; water completes the copper coordination sphere. The dinuclear complex cocrystallizes with a mononuclear Cu-dpp-ox complex; in the mixed crystal two mononuclear units replace one dinuclear unit in 25% of the unit cells, thus the average formula is [Cu 2(ddpp)(ox) 2(H 2O) 2] 0.75[{Cu(dpp)(ox)(H 2O)} 2] 0.25·8H 2O ( 5). The monomeric species also crystallizes in the form of compound