Determination of Cu3+, Bi5+ and Pb4+ in high Tc superconducting oxides by Cl2 generation, or by O2 together with Cl2 generation

Summary For estimating the values corresponding to the oxygen defects in high T_c superconducting oxides, iodometry has been applied for the determination of Cu³⁺ and Cu²⁺. The presence of Bi or Pb causes some difficulty in the identification of the end point of this titration, because of the formation of iodine complexes. Therefore, chlorine generation from HCl and iodometry was applied for the determination of Bi⁵⁺ or Pb⁴⁺ in the oxides, and for the additional determination of Cu³⁺, O₂ generation was used together with Cl₂ generation for Bi⁵⁺ or Pb⁴⁺.     

Dendrimers with Porphyrin Cores: Synthetic models for globular heme proteins

Dendritic iron porphyrins were synthesized as functional mimics of globular electron-transfer heme proteins. The cascade molecules 1 · Zn ? 3 Zn of first to third generation were obtained starting from the (meso-diarylporphyrin) zinc 6 · Zn which contains four carboxylate arms for attachment of the poly(ether-amide) dendritic branches by peptide-coupling methodology (Scheme 1). Generation 3 compound 3 · Zn with 108 methyl-carboxylate end groups has a molecular weight of 19054. D, and computer modeling suggests that its structure is globular and densely-packed, measuring ca. 4 nm in diameter and, therefore, similar in dimensions to the electron-transfer protein cytochrome-c. Starting from the generation 1 poly(carboxylic acid) 11 · Zn and the generation 2 analog 12 · Zn the dendritic Zn^II porphyrins 4 · Zn and 5 · Zn , respectively, were obtained by esterification with triethyleneglycol monomethyl ether (Schemes 3 and 4). Demetallation followed by insertion of Fe^II and in situ oxidation afforded the water-soluble dendritic iron porphyrins 4 FeCl and 5 FeCl . The electrochemical behavior of esters 1 · Zn ? 3 · Zn in organic solvents changed smoothly with increasing dendritic generation (Table 1). Progressing from 1 · Zn to 3 · Zn in THF, the first porphyrin-centered oxidation and reduction potentials become more negative by 320 and 210mV, respectively. These changes were attributed to strong microenvironmental effects imposed on the electroactive core by the densely packed dendritic surroundings. The electrochemical properties of 4 · FeCl and 5 · FeCl were investigated by cyclic voltammetry in both CH₂Cl₂ and H₂O (Tables 2 and 3). Progressing from 4 · FeCl to 5 · FeCl in CH₂Cl₂, the redox potential of the biologically relevant Fe^III/Fe^II couple remained virtually unchanged, whereas in aqueous solution, 5 FeCl exhibited a potential 420 mV more positive than did 4 FeCl. The large difference between these potentials in H₂O was attributed to differences in solvation of the core electrophore. Whereas the relatively open dendritic branches in 4 · Fecl do not impede access of bulk solvent to the central core, the densely packed dendritic superstructure of 5 · FeCl significantly reduces contact between the heme and external solvent. As a result, the more charged Fe^III state is destabilized relative to Fe^II, and the redox potential is strongly shifted to a more positive value.     

A SHG-active manganese coordination polymer with noncentrosymmetric structure based on achiral carboxyphosphinate ligand

The hydrothermal reaction of MnSO₄ with the achiral 2-carboxyethyl(phenyl)phosphinate ligand (H₂L) afforded a 2?D coordination polymer manganese phosphinate, [Mn(HL)₂]_n (1) (H₂L?=?2-carboxyethyl(phenyl) phosphinic acid). It contains two types of dimeric ring motifs, which can generate a layer structure through edge-sharing. The interlayer stacking by C-H…π interactions between the C-H groups of the phenyl rings of HL^- and the phenyl rings of the adjacent layers results in its crystallization in a noncentrosymmetric crystal structure with (4³)₂(4⁶·6⁶·8³) topology. Compound 1 shows a second harmonic generation response that is 0.8 times that of urea. The luminescence spectrum indicates an emission maximum at 457?nm, attributed to an intra-ligand emission state.     

Metal–Organic Framework (MOF)-Derived Electron-Transfer Enhanced Homogeneous PdO-Rich Co3O4 as a Highly Efficient Bifunctional Catalyst for Sodium Borohydride Hydrolysis and 4-Nitrophenol Reduction

Developing a bifunctional catalyst with low cost and high catalytic performance in NaBH₄ hydrolysis for H₂ generation and selective reduction of nitroaromatics will make a significant impact in the field of sustainable energy and water purification. Herein, a low-loading homogeneously dispersed Pd oxide-rich Co₃O₄ polyhedral catalyst (PdO-Co₃O₄) with concave structure is reported by using a metal–organic framework (MOF)-templated synthesis method. The results show that the PdO-Co₃O₄ catalyst has an exceptional turnover frequency (3325.6 mol_H2 min⁻¹ mol_Pd⁻¹), low activation energy (43.2 kJ mol⁻¹), and reasonable reusability in catalytic H₂ generation from NaBH₄ hydrolysis. Moreover, the optimized catalyst also shows excellent catalytic performance in the NaBH₄ selective reduction of 4-nitrophenol to 4-aminiphenol with a high first-order reaction rate of approximately 1.31 min⁻¹. These excellent catalytic properties are mainly ascribed to the porous concave structure, monodispersed Pd oxide, as well as the unique synergy between PdO and Co₃O₄ species, which result in a large specific surface area, high conductivity, and fast solute transport and gas emissions.     

Directional Potassium Transport through a Unimolecular Peptide Channel

Three unimolecular peptide channels have been designed and prepared by using the β‐helical conformation of gramicidin A (gA). The new peptides bear one to three NH₃⁺ groups at the N‐end and one to three CO₂^? groups at the C‐end. These zwitterionic peptides were inserted into lipid bilayers in an orientation‐selective manner. Conductance experiments on planar lipid bilayers showed that this orientation bias could lead to observable directional K⁺ transport under multi‐channel conditions. This directional transport behavior can further cause the generation of a current across a planar bilayer without applying a voltage. More importantly, in vesicles with identical external and internal KCl concentrations, the channels can pump K⁺ across the lipid bilayer and cause a membrane potential.     

Poly(10-undecene-1-ol) characterized by MALDI-TOF MS and NMR spectroscopy

Poly(10-undecene-1-ol)s were synthesized by metallocene-catalyzed polymerization. MALDI-TOF MS allows obtaining detailed information on the monomer units in the polymer chains and the nature of the head and end groups of these polymers in dependence on the Al alkyl triisobutyl aluminum (TIBA) as well as methylalumoxan (MAO), both used as protecting agent for the hydroxyl groups of the monomer. The peak-to-peak distances of the main peaks could be distinctly assigned to the monomer unit 10-undecene-1-ol. Evaluating the MALDI-TOF peak distributions, polymers with -H, -C₄H₉, -CH₃ head groups in combination with vinylidene and saturated (–CH₃) end groups could be detected. By ¹H NMR spectroscopy, it was verified that with the used catalysts polymers with vinylidene end groups were obtained predominantly. The presence of saturated end groups could be proved qualitatively by combination of ¹H and ¹³C NMR spectroscopy for polymers produced by TIBA protection, which strikingly confirm the results from MALDI-TOF MS. For the polymers prepared with only MAO protection, saturated groups are also proved but discrimination between head and end groups was not possible. A polymerization mechanism corresponding to the detected different head and end groups is proposed.     

Hydrogen bonding in two ammonium salts of 5‐sulfosalicylic acid: ammonium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate and triammonium 3‐carboxy‐4‐hydroxybenzenesulfonate 3‐carboxylato‐4‐hydroxybenzenesulfonate

The structures of two ammonium salts of 3‐carboxy‐4‐hydroxybenzenesulfonic acid (5‐sulfosalicylic acid, 5‐SSA) have been determined at 200 K. In the 1:1 hydrated salt, ammonium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate, NH₄⁺·C₇H₅O₆S⁻·H₂O, (I), the 5‐SSA⁻ monoanions give two types of head‐to‐tail laterally linked cyclic hydrogen‐bonding associations, both with graph‐set R₄⁴(20). The first involves both carboxylic acid O—H...O_water and water O—H...O_sulfonate hydrogen bonds at one end, and ammonium N—H...O_sulfonate and N—H...O_carboxy hydrogen bonds at the other. The second association is centrosymmetric, with end linkages through water O—H...O_sulfonate hydrogen bonds. These conjoined units form stacks down c and are extended into a three‐dimensional framework structure through N—H...O and water O—H...O hydrogen bonds to sulfonate O‐atom acceptors. Anhydrous triammonium 3‐carboxy‐4‐hydroxybenzenesulfonate 3‐carboxylato‐4‐hydroxybenzenesulfonate, 3NH₄⁺·C₇H₄O₆S²⁻·C₇H₅O₆S⁻, (II), is unusual, having both dianionic 5‐SSA²⁻ and monoanionic 5‐SSA⁻ species. These are linked by a carboxylic acid O—H...O hydrogen bond and, together with the three ammonium cations (two on general sites and the third comprising two independent half‐cations lying on crystallographic twofold rotation axes), give a pseudo‐centrosymmetric asymmetric unit. Cation–anion hydrogen bonding within this layered unit involves a cyclic R₃³(8) association which, together with extensive peripheral N—H...O hydrogen bonding involving both sulfonate and carboxy/carboxylate acceptors, gives a three‐dimensional framework structure. This work further demonstrates the utility of the 5‐SSA⁻ monoanion for the generation of stable hydrogen‐bonded crystalline materials, and provides the structure of a dianionic 5‐SSA²⁻ species of which there are only a few examples in the crystallographic literature.     

Formation of poly(ethylene phosphates) in polycondensation of H3PO4 with ethylene glycol. Kinetic and mechanistic study

Conditions of synthesis of poly(ethylene phosphates) in reaction of H₃PO₄ with HOCH₂CH₂OH (EG), the actual path of polycondensation, and structure of the obtained polymers (mostly oligomers) and kinetics of reaction are described. Preliminary kinetic information, based on the comparison of the MALDI‐TOF‐ms and ³¹P{¹H} NMR spectra as a function of conversion is given as well. Because of the dealkylation process fragments derived from di‐ and triethylene glycols are also present in the repeating units. Structures of the end groups (? CH₂CH₂OH or ? OP(O)(OH)₂) depend on the starting ratio of [EG]₀/[H₃PO₄]₀, although even at the excess of EG the acidic end groups prevail because of the dealkylation process. In MALDI‐TOF‐ms products with P_n equal up to 21 have been observed. The average polymerization degrees (P_n) are lower and have been calculated from the proportion of the end groups. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 830–843, 2008     

catena‐Poly[thorium(IV)‐tetrakis(μ2‐3‐carboxyadamantane‐1‐carboxylato)]: a quadruple helical strand driven by a synergy of coordination and hydrogen bonding

The title compound, [Th(C₁₂H₁₅O₄)₄]_n, is the first homoleptic thorium–carboxylate coordination polymer. It has a one‐dimensional structure supported by the bidentate bridging coordination of the singly charged 3‐carboxyadamantane‐1‐carboxylate (HADC⁻) anions. The metal ion is situated on a fourfold axis (site symmetry 4) and possesses a square‐antiprismatic ThO₈ coordination, including four bonds to anionic carboxylate groups [Th—O = 2.359 (2) Å] and four to neutral carboxyl groups [Th—O = 2.426 (2) Å], while a strong hydrogen bond between these two kinds of O‐atom donor [O...O = 2.494 (3) Å] affords planar pseudo‐chelated Th{CO₂...HO₂C} cycles. This combination of coordination and hydrogen bonding is responsible for the generation of quadruple helical strands of HADC⁻ ligands, which are wrapped around a linear chain of Th^IV ions [Th...Th = 7.5240 (4) Å] defining the helical axis.     

Extension of the chain‐end,free‐volume theory for predicting glass temperature as a function of conversion in hyperbranched polymers obtained through one‐pot approaches

Compared with linear polymers, more factors may affect the glass‐transition temperature (T_g) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. T_g's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of T_g to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. T_g's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. T_g values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. T_g values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of T_g versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that T_g increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004     

Cationic polymerizations by aromatic initiating systems. V. Oxidation and chlorination of α,ω-diphenylpolyisobutylene and subsequent reaction with living polystyrene anions to form block copolymers

α,ω-Diphenylpolyisobutylenes produced by the Cl^t-R-Cl^t/ø₃Al initiating system have been derivatized. Model chloromethylation of t-butylbenzene by CH₃OCH₂Cl in chloroform indicated that beyond ca. 35% yield significant alkylative side reactions occurred. Phenyl end groups (average 1.5 per chain) and unsaturated chain ends (from proton elimination) have been converted to carboxyl end groups by oxidation with RuO₄ in chloroform. Subsequently the carboxyl end groups were converted to acyl chloride termini by reaction with SOCl₂. The latter end groups were coupled with living polystyryl anions to form isobutylene-styrene blcok copolymers.     

The lock‐in phase in the urotropine–sebacic acid system

The 1,10‐decane­dioic acid–1,3,5,7‐tetra­aza­tri­cyclo­[3.3.1.1^3,7]­decane (1/1) system, C₁₀H₁₈O₄·C₆H₁₂N₄, was studied at 215 (2) K. Its analysis provides important information with regard to the long‐standing acid–carboxyl­ate controversy in the urotropine–alkanedioic acid system. In the present structure, all the chain end‐groups display a clear acid character. The asymmetric unit of this commensurate modulated phase contains two mol­ecules of diacid as well as two mol­ecules of urotropine. Furthermore, the chain packing suggests a possible order parameter for the lock‐in transition.     

Quantenchemische Modellrechnungen zur Baugruppenwanderung in Hexafluorosilicaten

Quantum Chemical Model Calculations on the Migration of Si? F Groups in Hexafluorosilicates The transport of different Si? F species was simulated using two [SiF₆]^2? octahedra as example. Activation barriers and charge distributions were calculated with the EHT method. Bearing in mind the structure of cubic hexafluorosilicates calculations were carried out on the migration both along an edge and along a (110) face of the elementary cell. At first [SiF₂]²⁺ and SiF₄ groups were removed from an [Si₂F₁₂]^4? unit to produce a surface vacancy. During a second step planar SiF₄ groups were moved to the neighbouring lattice position. A diffusion of planar SiF₄ is favoured, if the electrostatic interaction between moved and fixed fluorine atoms is as small as possible.     

Crystal Structure of Cesium Phenylacetylide,CsC2C6H5, Solved and Refined from Synchrotron Powder Diffraction Data

The crystal structure of cesium phenylacetylide, CsC₂C₆H₅, was solved and refined from synchrotron powder diffraction data (Pbca, Z = 8). Each Cs⁺ cation is coordinated by five ligands: four acetylide groups coordinate side‐on and one end‐on. A similar arrangement is found in the crystal structure of NaC₂H (P4/nmm, Z = 2). There is a group‐subgroup relationship between both structures. Most importantly, the crystal structure of CsC₂C₆H₅ could only be solved with the help of synchrotron data, as the very good peak:noise ratio allowed the assignment of several very weak reflections, which finally led to the correct space group, in which a structural solution was possible using direct space methods.     

A non‐linear optical crystal,Cd3Zn3(BO3)4

The title compound, tricadmium trizinc tetraborate, Cd₃Zn₃(BO₃)₄, is a new non‐linear optical (NLO) crystal and its structure has been determined by single‐crystal X‐ray diffraction. This compound is composed of planar [BO₃]³⁻ groups sharing O atoms with CdO₄ or ZnO₄ tetrahedra. The BO₃ triangles are located on threefold axes and are arranged with nearly the same orientation. The Cd and Zn atoms are disordered on the same site in the proportion 1:1. A strong second harmonic generation of Nd:YAG laser radiation (λ = 1064 nm) has been observed for a crystal of the title compound.     

Preparation of Polylactide Microspheres Having Positively or Negatively Charged Surfaces

The syntheses of polylactides (PLAs) with branched peptide end groups containing reactive (ionic) moieties such as amino or carboxyl groups are described and were used to prepare PLA‐based microspheres (MSs) with positively or negatively charged surfaces. Branched peptides with hydroxyl end groups and four protected amino or carboxyl groups, Boc₄‐K₃‐OH or Bn₄‐E₃‐OH, were synthesized, and the hydroxyl group converted to an alkoxide and was used as the initiation site for the ring‐opening polymerization of L ‐lactide. Subsequent deprotection gave PLAs end‐capped with branched peptides having four amino or carboxyl groups, respectively (K₃‐PLA and E₃‐PLA). K₃‐PLA and E₃‐PLA were converted to K₃⁴⁺‐PLA and E₃^4?‐PLA by acid or base treatment, respectively. MSs with charged surfaces were then prepared using K₃⁴⁺‐PLA or E₃^4?‐PLA as a surfactant [MS(K₃⁴⁺‐PLA) or MS(E₃^4?‐PLA)]. The ionic surface state of the MSs was confirmed by colloidal titration and zeta potential analysis.

SEM image of MSs: MS(K₃⁴⁺‐PLA).     

On the difference of reactivities of various aggregated forms of aluminium triisopropoxide in initiating ring-opening polymerizations

The polymerization of ε-caprolactone (εCL) initiated with aluminium triisopropoxide (Al(OⁱPr)₃) trimer ( A ₃) and/or tetramer ( A ₄) was studied. The rate of A ₃ ⇔︁ A ₄ interconversions in the diluted (≤0,1 mol · L^-1) C₆D₆, C₆D₆/εCL, and THF/εCL solutions were found to be slow, when compared with the rate of propagation. Comparison of the ¹H NMR spectra of the initiators with those of the polymerization mixtures revealed that A ₃ is much more reactive than A ₄ in their reactions with εCL. From the initiator reacted with εCL all threeOⁱPr groups from Al(OⁱPr)₃ are transferred into the poly(εCL) as end groups. Kinetic studies of polymerization confirmed the large reactivity difference between A ₃ and A ₄.     

Dual Functioning Thieno‐Pyrrole Fused BODIPY Dyes for NIR Optical Imaging and Photodynamic Therapy: Singlet Oxygen Generation without Heavy Halogen Atom Assistance

We discovered a rare phenomenon wherein a thieno‐pyrrole fused BODIPY dye (SBDPiR690) generates singlet oxygen without heavy halogen atom substituents. SBDPiR690 generates both singlet oxygen and fluorescence. To our knowledge, this is the first example of such a finding. To establish a structure–photophysical property relationship, we prepared SBDPiR analogs with electron‐withdrawing groups at the para‐position of the phenyl groups. The electron‐withdrawing groups increased the HOMO–LUMO energy gap and singlet oxygen generation. Among the analogs, SBDPiR688, a CF₃ analog, had an excellent dual functionality of brightness (82290 m ^?1 cm^?1) and phototoxic power (99170 m ^?1 cm^?1) comparable to those of Pc 4, due to a high extinction coefficient (211 000 m ^?1 cm^?1) and balanced decay (Φ_flu=0.39 and Φ_Δ=0.47). The dual functionality of the lead compound SBDPiR690 was successfully applied to preclinical optical imaging and for PDT to effectively control a subcutaneous tumor.     

Alleviating Side Reactions on Zn Anodes for Aqueous Batteries by a Cell Membrane Derived Phosphorylcholine Zwitterionic Protective Layer

Aqueous zinc (Zn) ion batteries are attractive for next generation batteries with high safety, yet their applications are still hindered by the uncontrollable dendrite formation and side reactions on Zn anode. Here, a polyzwitterion protective layer (PZIL) was engineered by polymerizing 2-methacryloyloxyethyl phosphorylcholine (MPC) in carboxymethyl chitosan (CMCS), which renders the following merits: the choline groups of MPC can preferentially adsorb onto Zn metal to avoid side reactions; the charged phosphate groups chelate with Zn²⁺ to regulate the solvation structure, further improving side reaction inhibition; the Hofmeister effect between ZnSO₄ and CMCS can enhance the interfacial contact during electrochemical characterization. Consequently, the symmetrical Zn battery with PZIL can keep stable for more than 1000 hours under the ultra-high current density of 40 mA cm⁻². The PZIL confers the Zn/MnO₂ full battery and Zn/active carbon (AC) capacitor with stable cycling performance under high current density.     

Metal Fluorides as Analogues for Studies on Phosphoryl Transfer Enzymes

The 1994 structure of a transition‐state analogue with AlF₄⁻ and GDP complexed to G1α, a small G protein, heralded a new field of research into the structure and mechanism of enzymes that manipulate the transfer of phosphoryl (PO₃⁻) groups. The number of enzyme structures in the PDB containing metal fluorides (MF_x) as ligands that imitate either a phosphoryl or a phosphate group was 357 at the end of 2016. They fall into three distinct geometrical classes: 1) Tetrahedral complexes based on BeF₃⁻ that mimic ground‐state phosphates; 2) octahedral complexes, primarily based on AlF₄⁻, which mimic “in‐line” anionic transition states for phosphoryl transfer; and 3) trigonal bipyramidal complexes, represented by MgF₃⁻ and putative AlF₃⁰ moieties, which mimic the geometry of the transition state. The interpretation of these structures provides a deeper mechanistic understanding into the behavior and manipulation of phosphate monoesters in molecular biology. This Review provides a comprehensive overview of these structures, their uses, and their computational development.