The crystal and molecular structure of potassium aquapentachloroiridate(III) and the H, C, N NMR coordination shifts in iridium(III) chloride complexes with 2,2′-bipyridine or 1,10-phenanthroline

The crystal and molecular structure of potassium aquapentachloroiridate(III) (K₂[Ir(H₂O)Cl₅]) was reported. The [Ir(H₂O)Cl₅]²⁻ anions are nearly octahedral, the axial Ir–Cl bond (2.322(2) Å) being shorter than the equatorial ones (2.346(2)–2.360(2) Å); the Ir–O bond length is 2.090(4) Å. Ir(III) chloride complexes with 2,2′-bipyridine (LL = bpy) or 1,10-phenanthroline (LL = phen), of the general formulae K[Ir(LL)Cl₄] and cis-[Ir(LL)₂Cl₂]Cl, were studied by far-IR and ¹H–¹³C, ¹H–¹⁵N HMBC/HMQC/HSQC–NMR. High-frequency ¹H NMR coordination shifts (Δ^1H_coord = δ^1H_complex − δ^1H_ligand; max. ca. +1 ppm) were noted for [Ir(LL)Cl₄]⁻ anions, while for cis-[Ir(LL)₂Cl₂]⁺ cations they had variable sign and magnitude (max. ca. ±1 ppm); they were dependent on the proton position, being mostly expressed for the nitrogen-adjacent hydrogens (H(6) for bpy, H(2) for phen). ¹³C NMR signals were high-frequency shifted (by max. ca. 8 ppm), whereas all ¹⁵N nuclei were shifted to the lower frequency (by ca. 105–120 ppm). The experimental ¹H, ¹³C, ¹⁵N NMR chemical shifts were reproduced by semi-empirical quantum-chemical calculations (B3LYP/LanL2DZ+6-31G^**//B3LYP/LanL2DZ+6-31G*).     

On nonatomic submeasures on . II

It is shown that if two submeasures on that are lim sup's of sequences of measures have the same zero sets, and one is nonatomic, so is the other, and they are (ε-δ)-equivalent. Moreover, if a submeasure η is the lim sup of a sequence of lower semi-continuous (lsc) submeasures and is 0-dominated by the so-called core γ^• of an lsc submeasure γ, then η is also (ε-δ)-dominated by γ^•. And if a submeasure η of this type is 0-dominated by a nonatomic submeasure, then it is nonatomic as well.     

Gold nanoparticle chemiresistors operating in biological fluids

Functionalised gold nanoparticle (Au(NP)) chemiresistors are investigated for direct sensing of small organic molecules in biological fluids. The principle reason that Au(NP) chemiresistors, and many other sensing devices, have limited operation in biological fluids is due to protein and lipid fouling deactivating the sensing mechanism. In order to extend the capability of such chemiresistor sensors to operate directly in biofluids, it is essential to minimise undesirable matrix effects due to protein and lipidic components. Ultrafiltration membranes were investigated as semi-permeable size-selective barriers to prevent large biomolecule interactions with Au(NP) chemiresistors operating in protein-loaded biofluids. All of the ultrafiltration membranes protected the Au(NP) chemiresistors from fouling by the globular biomolecules, with the 10 kDa molecular weight cut-off size being optimum for operation in biofluids. Titrations of toluene in different protein-loaded fluids indicated that small molecule detection was possible. A sensor array consisting of six different thiolate-functionalised Au(NP) chemiresistors protected with a size-selective ultrafiltration membrane successfully identified, and discriminated the spoilage of pasteurised bovine milk. This proof-of-principle study demonstrates the on-chip protein separation and small metabolite detection capability, illustrating the potential for this technology in the field of microbial metabolomics. Overall, these results demonstrate that a sensor array can be protected from protein fouling with the use of a membrane, significantly increasing the possible application areas of Au(NP) chemiresistors ranging from the food industry to health services.     

Thermal properties of potassium bis(oxalato)diaquochromates(III) in solid state. Trans–cis isomerization of the [Cr(C2O4)2(OH2)2]? complex ion in aqueous solutions

The thermal decomposition of trans-K[Cr(C₂O₄)₂(OH₂)₂]·3H₂O and cis-K[Cr(C₂O₄)₂(OH₂)₂] has been studied using the TG–MS technique. The measurements were carried out in an argon atmosphere over the temperature range of 293–873 K. The influence of the complex structures and configurational geometry on the stability of the transition products and the pathways of thermal transformations has been discussed. Furthermore, the kinetics of the isomerization reactions of the [Cr(C₂O₄)₂(OH₂)₂]⁻ complex ion catalyzed by five different metal ions: Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ have been studied. The isomerization reactions were studied in aqueous solution at five various temperatures (283–303 K), at constant concentration of metal ions (C = 0.1 M) and the constant ionic strength of solution (Na⁺, NO₃ ⁻) I = 2.4 M. The rates of the isomerization reaction were determined spectrophotometrically by monitoring of absorbance changes at 410 nm.     

Dioxygen Oxidation Cu(II) → Cu(III) in the Copper Complex of cyclo(Lys-dHis-βAla-His): A Case Study by EXAFS and XANES Approach

A former spectroscopic study of Cu(II) coordination by the 13-membered ring cyclic tetrapeptide c(Lys-dHis-βAla-His) (DK13), revealed the presence, at alkaline pH, of a stable peptide/Cu(III) complex formed in solution by atmospheric dioxygen oxidation. To understand the nature of this coordination compound and to investigate the role of the His residues in the Cu(III) species formation, Cu K-edge XANES, and EXAFS spectra have been collected for DK13 and two other 13-membered cyclo-peptides: the diastereoisomer c(Lys-His-βAla-His) (LK13), and c(Gly-βAla-Gly-Lys) (GK13), devoid of His residues. Comparison of pre-edge peak features with those of Cu model compounds, allowed us to get information on copper oxidation state in two of the three peptides, DK13 and GK13: DK13 contains only Cu(III) ions in the experimental conditions, while GK13 binds only with Cu(II). For LK13/Cu complex, EXAFS spectrum suggested and UV-vis analysis confirmed the presence of a mixture of Cu(II) and Cu(III) coordinated species. Theoretical XANES spectra have been calculated by means of the MXAN code. The good agreement between theoretical and experimental XANES data collected for DK13, suggests that the refined structure, at least in the first coordination shell around Cu, is a good approximation of the DK13/Cu(III) coordination species present at strongly alkaline pH. All the data are consistent with a slightly distorted pyramidal CuN(4) unit, coming from the peptide bonds. Surprisingly, the His side-chains seemed not involved in the final, stable, Cu(III) scaffold.     

The initial boundary value problem for the nonlinear parabolic equation in unbounded domain

In this paper we consider the mixed problem for the equation u _tt  + A ₁ u + A ₂(u _t ) + g(u _t ) = f(x, t) in unbounded domain, where A ₁ is a linear elliptic operator of the fourth order and A ₂ is a nonlinear elliptic operator of the second order. Under natural assumptions on the equation coefficients and f we proof existence of a solution. This result contains, as a special case, some of known before theorems of existence. Essentially, in difference up to previous results we prove theorems of existence without the additional assumption on behavior of solution at infinity.