Electronic structures of collagen model polymers: (Gly-Pro)n, (Gly-Hyp)n, (Ala-Pro)n, (Ala-Hyp)n, (Gly-Pro-Gly)n, (Gly-Hyp-Gly)n, (Gly-Pro-Pro)n, and (Gly-Pro-Hyp)n

In order to investigate the relationship existing between the electronic structures of collagen and its biochemical functions in vivo, the semiempirical CNDO/2 SCF MO calculations were carried out on several model polymers of collagen, (Gly-Pro)_n, (Gly-Hyp)_n, (Ala-Pro)_n, (Ala-Hyp)_n, (Gly-Pro-Gly)_n, (Gly-Hyp-Gly)_n, (Gly-Pro-Pro)_n and (Gly-Pro-Hyp)_n. Geometries of the skeleton of these polymers were assumed to be the same as those of poly(l-proline) I (cis) and II (trans) and the calculations were performed only on infinite polymers in a single chain. The results show that the cis form is always more stable than the trans form for all the polymers treated. This energy difference between the cis and trans forms depends, for example, on the kind of amino acid residue, Gly or Ala, but this could not be seen in the Pro or Hyp residue. The flexibility or mobility of the collagen structure was explained using the energy difference between the cis and trans forms of the polymers, i.e. the cis-trans conversion of the collagen was discussed in connection with the energy difference. The reason why the collagen has the constitution of (Gly-Pro-Hyp)_n is briefly discussed.     

Structure determination of the 2:1 derivatives of copper(I) bromide and iodide with bis(diphenylphosphino)methane. A simple structural scheme for the formation of (CuX)nLm species

The structures of the complexes (CuX)₂DPM (X = Br, I; DMP = bis(diphenylphosphino)methane) were determined from three dimensional X-ray data collected by counter methods. The iodine derivative crystallizes in the space group Pbca with eight units in a cell defined by a = 17.128(9), b = 18.306(9) c, = 16.508 (8) Å. The structure was refined by the least-squares method to a final R factor of 0.054 for 1336 non-zero independent reflections. The bromine derivative crystallizes in the space group P2₁/c with eight units in a cell defined by a = 23.707(1), b = 17.805(9), c = 16.991(1) Å, β = 136.10(5)°. The final least-squares refinement, based on 2489 non-zero independent reflections, gave an R factor of 0.074.Both the compounds have similar structures with a centrosymmetric (CuX)₄ core, in which two copper atoms have a tetrahedral geometry, while the other two are trigonal.The above structures are compared with those already reported for other compounds (CuX)_nL_m and a single scheme is proposed to rationalize the different geometries of the (CuX)_n core on the basis of steric and electronic effects.     

A family of double helices of alternating poly(gamma-benzyl-D-L-glutamate), a stereochemical model for gramicidin A.

Poly(γ-benzyl-d-l-glutamate) with strict alternation of l and d residues is found to exist, in addition to the α_DL and π_DL^4.4 helical structures already described (Heitz et al., 1975a), in four more helical structures. Models based on double helices made of antiparallel strands are proposed for all four structures, based on infrared, X-ray and electron diffraction data. These double helices are, like the single-stranded π_DL helices, specific to polypeptides with a strict stereosequence of alternating l and d residues. The diameter of the helical core of three of these helices appears to depend on the dimensions of the solvent molecules. Conformational angles (located in the β regions) and atomic co-ordinates determined by conformational energy analysis are given for the four structures. Experimental conditions used to obtain these helices, and to induce transconformations between the various helical structures of PBd-lG are described. The present investigations on PBd-lG help to make more precise the structure and geometry of models proposed (Veatch et al., 1974) for the antibiotic gramicidin A.     

Cell attachment to a substratum and cell surface proteases.

The polytripeptide (Tyr-Ala-Glu)_n, n～-175, has been reported to undergo an α-helix-disordered chain transition in aqueous medium (Ramachandran, J., et al. (1971) Biopolymers, 10, 1829–1851). We find from circular dichroism and infrared spectroscopy that, upon transferring (Tyr-Ala-Glu)₉ from aqueous buffer at neutral pH to dioxane-containing media at acidic pH, and in certain other circumstances, a transition from the disordered state to the antiparallel β structure occurs. Molecular weight studies and the independence of the transition from concentration suggest that the β structure is intramolecular. (Tyr-Ala-Glu)₄ shows no evidence for the occurrence of any conformational change under similar conditions.     

Polynuclear complexes of copper(II) with the tetra-aza ligand 3,6-bis(2′-pyridyl)pyridazine(L). Crystal structure of the bromine derivative [Cu2L(OH)Br3]n

The tetra-aza ligand 3,6-bis(2′-pyridyl)pyridazine (L), when reacting in appropriate conditions with Cu(II) halides, gives rise to polynuclear complexes of general formula [Cu₂L(OH)X₃]_n (X = Cl or Br). The bromine derivative has been studied by X-ray analysis. The crystals are twins by merohedry of class I, space group Pn (P2₁/n apparent space group), with the following cell constants: a = 13.691(5), b = 6.245(3), c = 10.298(4) Å, β = 103.92(5)°. The structure was refined by least-squares techniques to a final R factor of 0.066. The structure consists of binuclear units joined to each other through bridging bromine atoms to form a polymeric array. The two independent copper atoms of the dinuclear moiety are five-coordinated with a geometry which is intermediate between a square-pyramid and a trigonal-bipyramid.     

Crystallographic data of the selenoenzyme glutathione peroxidase

Glutathione peroxidase prepared from bovine erythrocytes yields small, but well-ordered plate-like crystals. X-ray investigation shows them to belong to monoclinic space group C2. Unit cell dimensions are: $\text{a = 90.4}\text{A}\text{?}\text{, b = 109.5}\text{A}\text{?}\text{, c = 58.6}\text{A}\text{?}$, β = 99 ° ± 15 min. The crystal density is ?_c = 1.36 ± 0.02 g.cm^?3. Consequently, the asymmetric unit of the crystal cell is occupied by one tetrameric molecule of M_r 84,000. Matthew's (1968) parameter Γ_M is calculated to be 1.71 ų/dalton.     

Comparative structural studies of the first row early transition metal(III) chloride tetrahydrofuran solvates

Two compounds of empirical formula MCl₃- (THF)₃, M = V and Cr, have been characterized by single crystal X-ray studies. The VCl₃(THF)₃ molecule, which has a mer octahedral stereochemistry, crystallizes in the monoclinic space group P2₁/c with a= 8.847(2),b= 12.861(5),c= 15.134(3) Å, β = 91.94(2)°, V = 1721(1) ų and Z = 4. The V-Ci(1) and V-CI(2) distances have a mean value of 2.330 [3] Å while V-CI(3) = 2.297(2) Å, The VO(1) and VO(2) distances have a mean value of 2.061[8] Å while V-O(3) = 2.102(3) Å cis ClVCl angles average 92.0[5]° and cis OVO angles average 86.2[2]° . The isostmctural complex, CrCl₃(THF)₃, has a crystal structure made up of discrete octahedral mer-CrCl₃(THF)₃ molecules with the following unit cell dimensions (space group P2₁/c): a = 8.715(1), b= 12.786(3), c = 15.122(3) Å, β = 92.15(1)°, V = 1684(1) ų and Z = 4. The CrCl(1) and CrCl(2) distances have a mean value of 2.310131 Å while CrCl(3) = 2.283(2) Å. The CrO(1) and CrO(2) distances have a mean value of 2.0101171 Å while CrO(3) = 2.077(4) Å. cis ClCrCl angles average 90.9[4]° and cis OCrO angles average 86.1 [2]°. The structures of these two octahedral complexes and those previously reported for ScCl₃(THF)₃ and TiCl₃(THF)₃ are compared and certain general trends are discussed.     

Synthesis and characterization of four sequential glycyl/glutamate polypeptides

Poly(Glu(OBzl)-Gly)_n, poly(Glu-Gly)_n, poly(Gly)-(Glu(OBzl)-Gly), and poly(Gly-Glu-Gly) were synthesized from the pentachlorophenyl esters of the sequential monomer. Both of the polymers containing free glumatic-acid residues are soluble in water, as is the lower molecular weight fraction of the polytripeptides with the benzyl ester in place. Circular dichroism studies and infrared dichroism studies suggest that the 2₁ helix is favored for the polydipeptide with removal of the benzyl ester reducing the conformational integrity. The polytripeptide showed evidence of 3₁ helix in addition to the 2₁ form, depending on solvent. A rationale for the conformations observed is developed based on the bulkiness of the side-chain residues and conformational stabilization, in certain cases, by hydrophobic interactions between the benzyl ester groups.     

Probing the electronic structures and properties of neutral and charged arsenic sulfides [As n S2 (−1,0,+1), n = 1–6] with Gaussian-3 theory

The structures and energies of neutral and charged arsenic sulfides As _n S₂ ^(?1,0,+1) (n?=?1–6) were investigated systematically by means of the Gaussian-3 (G3) scheme. The ground-state structures of these species are presented. The ground-state structures of As _n S₂ can be viewed as the lowest-energy structure of neutral As _n+1S by replacing an As atom with a S atom. To be more precise, the ground-state structures of As _n S₂ can be viewed as the lowest-energy structure of neutral As _n+2 by replacing two As atoms with two S atoms, in which the feature of sulfur bonding is edge-bridging. No rule could be found for the ground state structure of As _n S₂ ^? and As _n S₂ ⁺. In As _n S₂ ^?, the feature of sulfur bonding is either edge-bridging or a terminal atom, and in As_nS₂ ⁺ the feature of sulfur bonding is edge-bridging analogous to As _n S₂. The potential energy surfaces of As₄S₂ and its charged species are very flat. So co-existence for many isomers of As₄S₂ and its charged species are possible. The reliable adiabatic electron affinities (AEAs) and adiabatic ionization potentials (AIPs) of As _n S₂ were estimated. There are odd-even alternations in both AEAs and AIPs as a function of size of As _n S₂. The dissociation energies (DEs) of S [and/or its ion S^(?/+)] from As _n S₂ clusters and their ions were calculated and used to reveal relative stability.     

The crystal and molecular structures of dioxo mo(VI) complexes of tripodal,tetradentate N,S-donor ligands

The crystal and molecular structures of the complexes MoO₂((SCH₂CH₂)₂NCH₂CH₂SCH₃), I and MoO₂((SCH₂CH₂)₂NCH₂CH₂N(CH₃)₂), II, have been determined from X-ray intensity data collected by counter methods. Compound I crystallizes in two forms, Ia and Ib. In form Ia the space group is P2₁/n with cell parameters a = 7.235(2), b = 7.717(2), c = 24.527(6) Å, β = 119.86(2)°, V = 1188(1) ų, Z = 4. In form Ib the space group is P2₁/c with cell parameters a = 14.945(5), b = 11.925(5), c = 14.878(4) Å, β = 114.51(2)°, V = 2413(3) ų, Z = 8. The molecules of I in Ia and Ib are very similar having an octahedral structure with cis oxo groups, trans thiolates (cis to both oxo groups) and N and thioether sulfur atoms trans to oxo groups. Average ditances are MoO = 1.70, MoS (thiolate) = 2.40, MoN = 2.40 and MoS (thioether) = 2.79 Å. Molecule II crystallizes in space group P2₁2₁2₁ with a = 7.188(1), b = 22.708(8), c = 7.746(2) Å, V = 1246(1) ų and Z = 4. The coordination about Mo is octahedral with cis oxo groups, trans thiolates and N atoms trans to oxo. Distances in the first coordination sphere are MoO = 1.705(2), 1.699(2), MoS = 2.420(1), 2.409(1) and MoN = 2.372(2), 2.510(2) Å. The conformational features of the complexes are discussed. Complex I displays MoO and MoS distances which are very similar to those found by EXAFS in sulfite oxidase. This similarity is discussed.     

Mononuclear rhodium(I) complexes of 4-Amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole. Crystal structure of [Rh(CO)2(NH2bpt)]ClO4

Reaction of 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (NH₂bpt) or its potassium salt (KNHbpt) with several rhodium(I) compounds, produces new neutral and cationic complexes of Rh(I). One of the complexes [Rh(CO)₂(NH₂bpt)]ClO₄ has been characterized by single-crystal X-ray diffraction. The crystals are monoclinic, space group P2₁/n, with a = 17.6130(6), b = 11.3072(2), c = 9.0013(2) Å, β = 101.536(2)° and Z = 4. The structure has been refined to R = 0.049.     

Studies on co-operative properties of tropomyosin-actin and tropomyosin-troponin-actin complexes by the use of N-ethylmaleimide-treated and untreated species of myosin subfragment 1

When subfragment-1 of rabbit skeletal myosin was extensively modified with N-ethylmaleimide, the protein became strongly associable to actin in the presence of MgATP at low ionic strength, while the ATPase ceased to be activated by actin. Various concentrations of the modified protein were mixed with 10 μmol of pure actin or actin complexed with tropomyosin, and the fraction β of actin saturated with the modified protein in each mixture was determined by an ultracentrifugal method. We then added 0.3 μmol of unmodified subfragment-1 to the same sets of mixtures as used in the above experiments and determined the rate of ATP hydrolysis V by unmodified subfragment-1 as a function of β. A biphasic V-β relation was obtained for the tropomyosin-actin complex: when β was increased continuously from zero, the rate first increased substantially, had a maximum value more than tenfold larger than the initial at β ～- 0.3, and finally decreased to zero. In contrast, the V-β profile for pure actin deviated downwards from a linear relation, showing that there was a weak repulsive interaction between the modified and unmodified subfragment-1 species bound to the actin filament. The occurrence of such a repulsion was interpreted in terms of a steric hinderance model. Assuming that the same kind of repulsion underlay the biphasic V-β relation for the tropomyosin-actin complex, we calculated the relation of V′-β in an ideal case where it was absent. The result was also biphasic. We studied regulated actin in the presence and absence of Ca²⁺ by the same method and obtained biphasic V′-β relations in both cases.The experimental results were analyzed by a two-state model based on the proposal of Bremel & Weber (1972) that, within tropomyosin-actin or the regulated actin complex, n actin monomers undergo “off”/“on” transitions as a unit. Interactions between units were ignored in order to estimate the apparent size n, as well as the equilibrium constant L for the transition in the absence of myosin heads. Within the framework of allosteric theory (Monod et al., 1965), we derived formulae fit for data analysis, found a satisfactory agreement of the experimental and theoretical results, and obtained values of n = 11, and L = 37 for the tropomyosin-actin complex, and n = 16, L = 9 for regulated actin in the presence of Ca²⁺. The parameters in its absence could not be determined separately from the V?β relation which, however, was well-approximated with a combination of n = 16 and L = 10,000. It was also shown that tropomyosin-actin complex in the “on” state activated subfragment-1 ATPase eightfold more strongly than pure actin, and 2.2 to 2.6-fold more strongly than regulated actin in the “on” state. The results are compared with those provided by Greene & Eisenberg (1980), Hill et al. (1980) and Trybus & Taylor (1980) and discussed in conjunction with the double helical structure of tropomyosin-actin and regulated actin filaments.A simple allosteric calculation is presented in the Appendix to explain the well-known biphasic dependence on substrate concentration of the rate of regulated actin-subfragment-1 MgATPase (Bremel et al., 1972; Weber & Murray, 1973), with a reference to Deshcherevsky (1977).     

New preparations and molecular structures of cis-MCl2(Ph2PCH2PPh2)2, M = Ru,Os and trans-RuCl2(Ph2PCH2PPh2)2

The title compounds were made by reacting bis(diphenylphosphino)methane (dppm) with reduced solutions of OsCl₆^4? and Ru₂OCl₁₀^4?. The crystal and molecular structures of these compounds have been determined form three-dimensional X-ray study. The cis-isomers crystallize with one CHCl₃ per molecule of the complex. All three compounds crystallize in the monoclinic space group P2₁/n with unit cell dimensions as follows: Cis-OsCl₂(dppm)₂·CHCl₃: a = 13.415(4) Å, b = 22.859(4) Å, c = 16.693(3) Å, β = 105.77(3)°, V = 4926(3) ų, Z = 4. cis-RuCl₂(dppm)₂·CHCl₃: a = 13.442(3) Å, b = 22.833(7) Å, c = 16.750(4) Å, β = 105.53(2)°, V = 4953(3) ų, Z = 4. trans-RuCl₂(dppm)₂: a = 11.368(7) Å, b = 10.656(6) Å, c = 18.832(12) Å; β = 103.90(6)°, V = 2213(7) ų; Z = 2. The structures were refined to R = 0.044 (R_w = 0.055) for cis-OsCl₂(dppm)₂·CHCl₃; R = 0.065 (R_w = 0.079) for cis-RuCl₂(dppm)₂·CHCl₃ and R = 0.028 (R_w = 0.038) for trans-RuCl₂(dppm)₂. The complexes are six coordinate with stable four-membered chelate rings. The PMP angle in the chelate rings is ca. 71° in each case.     

Synthesis and structures of porphyrin complexes of scandium: ClSc(TTP)·2(C 10H 7Cl) and O[Sc(TTP)] 2·6THF

A facile, high yield metallation procedure is reported for the insertion of Sc into H ₂(TTP) (TTP= dianion of meso-tetratolylporphyrin) using anhydrous ScCl ₃. Single crystal X-ray structures are reported for ClSc(TPP)·2(C ₁₀H ₇Cl) ( 1) and O[Sc(TTP)] ₂·6THF ( 2). Compound 1: space group P2 ₁/c with a = 19.850(17), b = 28.822(24), c = 9.954(9)Å, β = 95.71(7)°, Z = 4; 2: space group P2/n, a = 16.952(9), b = 16.737(5), c = 19.93(1)Å, β = 112.56(5)°, Z = 4. Compounds 1 and 2 both had large amounts of poorly ordered solvents in the lattice which resulted in rather high R factors in the range of 12–14%. In 1, the Sc is five-coordinate (4N and 1Cl) and is centered 0.68Åabove the plane defined by the four porphyrin nitrogens. For 2, the Sc is 0.82Åfrom the plane and contains a non-linear μ-oxide bridge with a ScO Sc angle of 109(3)°, but with essentially coplanar porphyrin rings.     

Synthesis and structure of chloro(ligand)bis(diphenylglyoximato)cobalt(III) complexes

The synthesis and characterization of trans-chloro- (ligand)bis(diphenylglyoximato)cobalt(III) complexes [ligand = pyridine (py), α-, β-, or γ-picoline (α-pic, β-pic, γ-pic), 3,5-lutidine (lut), p-toluidine (p-tol) and PPh₃] is presented. X-ray crystal structure determination of the pyridine (1) and p-toluidine (6) derivatives has been carried out. Compound 1 crystallizes in the monoclinic system, space group P2₁/n, with Z = 4 and unit cell parameters a = 23.124(4), b = 13.009(3) and c = 11.204(3) Å, and β= 93.14(2)°. Compound 6 crystallizes in the monoclinic system, space group P2₁/n, with Z = 4 and unit cell parameters a = 18.792(3), b = 12.540(2) and c = 15.346(3) Å, and β = 97.54(2)°.     

Preparation,structure and properties of dicyano silver complexes of the M(en)3Ag2(CN)4 and M(en)2Ag2(CN)4 type

Complexes of the M(en)₃Ag₂(CN)₄ (M = Ni, Zn, Cd) and M(en)₂Ag₂(CN)₄ (M = Ni, Cu, Zn, Cd) type were prepared and identified by elemental analysis, infrared spectroscopy, measurement of magnetic susceptibility, and X-ray powder diffractometry. The crystal structures of Ni(en)₃Ag₂(CN)₄ (I) and Zn(en)₂Ag₂(CN)₄ (II) were determined by the method of monocrystal structure analysis. Complex I crystallizes in the space group C2/c, a = 1.2639(5), b = 1.3739(4), c = 1.2494(4) nm, β = 113.25(4)°, D_m = 1.86(1), D_c = 1.86 gcm⁻³ Z = 4, R = 0.0429. The crystal structure of I consists of complex cations [Ni(en)₃]²⁺ and complex anions [Ag(CN)₂]⁻. Complex II crystallizes in the space group I2/m, a = 0.9150(3), b = 1.3308(4), c = 0.6442(2) nm, β = 95.80(3)°, D_m = 2.14(1), D_c = 2.15 gcm⁻³, Z = 2, R = 0.0334. Its crystal structure consists of infinite, positively charged chains of the [-NCAgCNZn- (en)₂]_nⁿ⁺ type and isolated [Ag(CN)₂]⁻ anions. The atoms of Ag are positioned parallely to the z axis and the AgAg distance is equal to 0.3221(2) nm.     

Studies on dithio-o-toluate copper(I) complexes with bis(diphenylphosphino)methane. Crystal structures of {di-μ3-dithio-o-toluato-S,S′,S′-bis[μ-bis(diphenylphosphino)methane-μ-dithio-o-toluato-S,S′]} tetracopper(I) and {di[μ-bis(diphenylphosphino)methane]bis(dithio-o-toluato-S,S′)} dicopper(I)

The structures of [(CuS₂CT)₂dppm]₂ (I) (T = o-tolyl; dppm = bis(diphenylphosphino)methane) and [CuS₂CTdppm]₂ (II) have been determined by X-ray methods. Crystals of I are monoclinic, space group P2₁/n, with a = 15.163(4), b = 18.691(5), c = 13.478(4) Å, β = 96.81(3)°, Z = 2; crystals of II are orthorhombic. space group Pccn, with a = 23.267(4), b = 13.016(3), c = 20.731(5) Å, Z = 4. The structures of I and II have been solved by Patterson and Fourier methods and refined by full-matrix least-squares to R = 0.082 for I and 0.092 for II. The structure of I consists of centrosymmetric tetranuclear complexes in which two pairs of Cu atoms are triply bridged by a dppm ligand and two dithiocarboxylate groups from the dithio-o-toluate ligands. These last behave differently: one of them through a sulphur atom is also bonded to a Cu atom of the other pair so forming a tetranuclear complex. The Cu atoms of each pair show different coordination: Cu(1) displays a distorted trigonal and Cu(2) a distorted trigonal pyramidal geometry. The structure of II consists of dimers, in which each copper atom, doubly bridged by two dppm ligands, completes a distorted trigonal pyramidal coordination through two sulphur atoms from dithio-o-toluate anions acting as chelating ligands. In both compounds the phenyl group of the dithio-o-toluate anions is orthogonal to the corresponding CS₂ group. Both complexes give methyldithio-o-toluate in high yields by reaction with methyl iodide.     

Tetra-, penta- and hexacoordinate copper(II) complexes with N3 donor isoindoline-based ligands: Characterization and SOD-like activity

Reaction of 1,3-bis(2′-Ar-imino)isoindolines (HLⁿ, n = 1-7, Ar = benzimidazolyl, N-methylbenzimidazolyl, thiazolyl, pyridyl, 3-methylpyridyl, 4-methylpyridyl, and benzthiazolyl, respectively) with Cu(OCH₃)₂ yields mononuclear hexacoordinate complexes with Cu(Lⁿ)₂ composition. With cupric perchlorate square-pyramidal [Cu^II(HLⁿ)(NCCH₃)(OClO₃)]ClO₄ complexes (n = 1, 3, 4) were isolated as perchlorate salts, whereas with chloride Cu^II(HLⁿ)Cl₂ (n = 1, 4), or square-planar Cu^IICl₂(HLⁿ) (n = 2, 3, 7) complexes are formed. The X-ray crystal structures of Cu(L³)₂, Cu(L⁵)₂, [Cu^II(HL⁴)(NCCH₃)(OClO₃)]ClO₄, Cu^IICl(L²) and Cu^IICl(L⁷) are presented along with electrochemical and spectral (UV-Vis, FT-IR and X-band EPR) characterization for each compound. When combined with base, the isoindoline ligands in the [Cu^II(HLⁿ)(NCCH₃)(OClO₃)]ClO₄ complexes undergo deprotonation in solution that is reversible and induces UV-Vis spectral changes. Equilibrium constants for the dissociation are calculated. X-band EPR measurements in frozen solution show that the geometry of the complexes is similar to the corresponding X-ray crystallographic structures. The superoxide scavenging activity of the compounds determined from the McCord-Fridovich experiment show dependence on structural features and reduction potentials.     

Synthesis and complexation studies of 16-membered [1+1] selenaaza- and some related macrocycles

A novel 16-membered [1+1] unsymmetrical selenaaza Schiff base macrocycle, 8,9,10,11-tetrahydo-7H-dibenzo-[d,o][1,3,7,10,13]diselenatriazacyclohexadecine (5) with N₃Se₂ donor set, has been synthesized by cyclocondensation of di(o-formylphenylseleno)methane and diethylenetriamine. Reduction of 5 with NaBH₄ afforded 6,7,8,9,10,11,12,13-octahydro-5H-dibenzo-[d,o][1,3,7,10,13]diselenatriazacyclohexadecine (6). Macrocycle, 10,11,12,13,14,15,16,26,27,28,29,30,31,32-tetradecahydrotetrabenzo[b,k,n,w][1,13,5,9,17,21]diselenatetraazacyclotetracosine (2b) was synthesized similarly from di(o-formylphenyl)selenide and 1,3-diaminopropane followed by reduction with NaBH₄. Single crystal X-ray structures of 5 and 2b have been determined. Attempted complexation reactions of 5 with Zn(II), Cd(II), Hg(II), Pd(II) and Cu(II) ions and those of 6 with Ag(I), Hg(II) and Pd(II) ions are reported. 28-Membered selenaaza macrocycle 2c on reaction with HgCl₂ and NH₄PF₆, provided a dinuclear Hg(II) complex 9. Complex 9 has been characterized by single crystal X-ray structure.     

Heterogeneity in branching of amylopectin

The angular dependence of scattered light from amylopectin and its β-limit dextrin, the mean square radius of gyration and the molecular weights M_w and M_n have been calculated on the basis of the cascade branching theory for the homogeneously branched model by Meyer &; Bernfeld (1940) (Model I) and for the two heterogeneously branched structures suggested by French (1972) (Model II) and by Robin et al. (1974, 1975) (Model III). The calculations take into account the particularities of topology in branched molecules and the experimentally determined ratio of the number of A- and B-chains, A/B = 1. Furthermore, an average branching density of 4% and an interconnecting chain length of ovbar|n_i2 = 22, found by gel permeation chromatography (GPC) after debranching, were used. The constraints lead to the conclusion that amylopectin is heterogeneously branched. Densely branched clusters containing 3·22 branching units are interconnected by longer chains of 22 units in length. Comparison of the calculated angular dependence of light scattering with measurements from a maize amylopectin β-limit dextrin in 1 n NaOH solution gives strong evidence for a modified Robin-Mercier model. The modification consists of the conclusion that the interconnecting chains are preferentially B-chains, such that these chains carry on the average 1·4 clusters, while Robin and Mercier assume exactly 2 clusters. Our result is in agreement with the distribution of chain length found after debranching the amylopectin β-limit dextrin.