Lanthanide complexes of [alpha-2-P2W17O61]10-: solid state and solution studies

We have isolated the 1:1 Ln:[alpha-2-P2W17O61]10- complexes for a series of lanthanides. The single-crystal X-ray structure of the Eu3+ analogue reveals two identical [Eu(H2O)3(alpha-2-P2W17O61)]7- moieties connected through two Eu-O-W bonds, one from each polyoxometalate unit. An inversion center relates the two polyoxometalate units. The Eu(III) ion is substituted for a [WO]4+ unit in the "cap" region of the tungsten-oxygen framework of the parent Wells-Dawson ion. The point group of the dimeric molecule is Ci. The extended structure is composed of the [Eu(H2O)3(alpha-2-P2W17O61)]214- anions linked together by surface-bound potassium cations. The space group is P, a = 12.7214(5) A, b = 14.7402(7) A, c = 22.6724(9) A, alpha = 71.550(3), beta = 84.019(3)degrees, gamma = 74.383(3), V = 3883.2(3) A3, Z = 1. The solution studies, including 183W NMR spectroscopy and luminescence lifetime measurements, show that the molecules dissociate in solution to form monomeric [Ln(H2O)4(alpha-2-P2W17O61)]7- species.     

Peptide synthesis under application of the 2-(p-diphenyl)-isopropyloxycarbonyn (Dpoc)-amino protection groups

The 2-(p-diphenyl)-isopropyloxycarbonyl (Dpoc) residue has been chosen for the selective protection of α-amino groups in the synthesis of peptides containing additional acid-labile protecting residues. It is easily introduced into amino-acids by reacting either the mixed carbonate I or the azide III with esters or salts of amino-acids. It is split by dilute acetic acid and other weakly acidic reagents at rates which permit a selective cleavage in the presence of other acid-labile protecting groups, especially those derived from t-butanol A number of peptide syntheses have been carried out with the new group either in the conventional manner or by the solid-phase method. No effects due to steric hindrance, as observed previously with the N-trityl residue, are encountered. The application of the Nα-Dpoc group to solid-phase peptide synthesis permits the use of a new combination of protecting groups in which the side chains of trifunctional amino-acids are blocked by acid-labile residues that can be easily split in the final step of the synthesis.     

Porphyrin Clathrates. Crystal Structures of Two Unexpected Products Obtained by Solvothermal Reactions of Pt-tetra(4-carboxyphenyl)porphyrin with Copper Acetate

The X-ray crystal structure of IX, perchlorate salt of R-(–-2-ethyl-N-benzyl-4,7,19,13-tetraoxa-8,9-benzo-1-azacyclopentadec-8-ene has been determined. In the molecule, the protonated nitrogen atom participates in two N-HO hydrogen bonds. The unusually high proton affinity of aza crown ether leads to the formation of diastreomer instead of complex formation with chiral R-(+)-1-phenyl ethyl ammonium perchlorate and S-(–)-1-phenyl ethyl ammonium perchlorate. The complex ability of host ethers was evaluated in terms of structural modification.     

Physicochemical characterization of phosphinic pseudopeptides by capillary zone electrophoresis in highly acidic background electrolytes

Phosphinic pseudopeptides (i.e., peptide isosteres with one peptide bond replaced by a phosphinic acid moiety) were analyzed and physicochemically characterized by capillary zone electrophoresis in the pH range of 1.1-3.2, employing phosphoric, phosphinic, oxalic and dichloroacetic acids as background electrolyte (BGE) constituents. The acid dissociation constant (pK(a)) of phosphinate group in phosphinic pseudopeptides and ionic mobilities of these analytes were determined from the pH dependence of their effective electrophoretic mobilities corrected to standard temperature and constant ionic strength of the BGEs. It was shown that these corrections are necessary whenever precise mobility data at very low pH are to be determined. Additionally, it was found that the ionic mobilities of the phosphinic pseudopeptides and pK(a) of their phosphinate group are affected by the BGE constituent used. The variability of migration behavior of the pseudopeptides can be attributed to their ion-pairing formation with the BGE components.     

Thermal behaviour of new N,N-dimethylbiguanide complexes having selective and effective antibacterial activity

The complexes of the type M(HDMBG)₂(CH₃COO)₂·nH₂O ((1) M:Mn, n=1.5; (2) M:Ni, n=0; (3) M:Cu, n=2; (4) M:Zn, n=2; DMBG: N,N-dimethylbiguanide) present in vitro antimicrobial activity. The thermal analysis has evidenced the thermal intervals of stability and also the thermodynamics effects that accompany them. The different nature of the ligands generates a different thermal behaviour for the complexes. The thermal transformations are complex processes according to TG and DTG curves including dehydration, oxidative condensation of –C=N– units as well as thermolysis processes. The final products of decomposition are the most stable metal oxides.     

Radon Measure-Valued Solutions for a Class of Quasilinear Parabolic Equations

Initial value problems for quasilinear parabolic equations having Radon measures as initial data have been widely investigated, looking for solutions which for positive times take values in some function space. In contrast, it is the purpose of this paper to define and investigate solutions that for positive times take values in the space of the Radon measures of the initial data. We call such solutions measure-valued, in contrast to function-valued solutionspreviously considered in the literature. We first show that there is a natural notion of measure-valued solution of problem (P) below, in spite of its nonlinear character. A major consequence of our definition is that, if the space dimension is greater than one, the concentrated part of the solution with respect to the Newtonian capacity is constant in time. Subsequently, we prove that there exists exactly one solution of the problem, such that the diffuse part with respect to the Newtonian capacity of the singular part of the solution (with respect to the Lebesgue measure) is concentrated for almost every positive time on the set where “the regular part (with respect to the Lebesgue measure) is large”. Moreover, using a family of entropy inequalities we demonstrate that the singular part of the solution is nonincreasing in time. Finally, the regularity problem is addressed, as we give conditions (depending on the space dimension, the initial data and the rate of convergence at infinity of the nonlinearity ψ) to ensure that the measure-valued solution of problem (P) is, in fact, function-valued.     

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO₂ electroreduction (CO₂R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO₂ reduction (CO₂R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO₂R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.