The role of the histidine residue in the coordination abilities of peptides with a multi-histidine sequence towards copper(II) ions

Cu²⁺ complexes with peptides containing three histidine residues have very specific metal binding abilities and can mimic the structures of various multi-histidine metal binding sites in proteins. The main goal of the work concerns the investigations of coordination abilities of the group of N-terminally protected Ac-His-Arg-His-Gly-His-Gly, Ac-His-Gly-His-Arg-His-Gly, Ac-Gly-His-His-Arg-His-Gly and Ac-His-His-Gly-His-Arg-Gly, and their unprotected analogs His-Arg-His-Gly-His-Gly, His-Gly-His-Arg-His-Gly, Gly-His-His-Arg-His-Gly and His-His-Gly-His-Arg-Gly towards Cu²⁺ ions. Detailed spectroscopic (UV/Vis, CD and EPR) and potentiometric studies have been made. The stoichiometry and binding mode for each ligand–Cu²⁺ system were determined.     

Neutron scattering study of the structural change induced by photopolymerization of AOT/D2O/dodecyl acrylate inverse microemulsions

Small-angle and ultrasmall-angle neutron scattering (SANS/USANS) measurements were used to determine the structural changes induced by photopolymerization of AOT/D2O/(dodecyl acrylate) inverse microemulsion systems. Scattering profiles were collected for the initial microemulsions and the films resulting from photopolymerization of the oil phase. The SANS data for the microemulsions were modeled as spherical, core-shell droplets. Upon polymerization, the clear mircoemulsions formed opaque films. From the SANS/USANS data of the films, it was apparent that this morphology was not preserved upon polymerization; however, it was clearly observed that the formulation of the microemulsion had a large impact on the structure within the films. The Guinier region in the USANS data (2.5 x 10(-5) A(-1) < or = Q < or = 5.3 x 10(-3) A(-1)) from the films indicates that very large structures are formed. Simultaneously, a well-defined peak (0.15 A(-1) < or = Q < or = 0.25 A(-1)) in the SANS data indicates that there are also much smaller structures formed. It is proposed that the low-Q scattering arises from aggregation of the nanometer-size water droplets in the microemulsion to form droplets large enough to scatter visible light, while the peak in the high-Q region results from bilayered structures formed by the surfactant.     

“Cap-Pair” Effect as the Reason of the Catalytic Properties of Nicotinic Acid: Experimental and Theoretical Studies

The influence of nicotinic acid (NC) on the kinetics and the mechanism of electroreduction of Zn²⁺ ions in the acetate buffer (pH=6.0) was investigated using electrochemical methods (EIS, CV, SWV and DC). It was shown that the anions of NC catalyze the electrode reaction (cap-pair effect) by adsorbing on the surface of the mercury electrode. The catalytic activity of NC is due to its ability to form active NC−Zn²⁺ complexes on the electrode surface, facilitating the electron transfer process. However, no evidence of the formation of such complexes in the solution was found using classical molecular dynamics. Moreover, it was proved that the electroreduction of Zn²⁺ ions in the presence of NC is a two-stage process. The first stage involves the transfer of the first electron, preceded by the partial loss of the hydration shell by the Zn²⁺ ions and formation of the active complex. Moreover, it was shown that in the range of lower concentrations, c≤1.10⁻² mol.dm⁻³, the nicotinic acid shows weaker catalytic abilities than another form of vitamin B3 – nicotinamide. In the range of its higher concentrations, the nicotinic acid is a more effective catalyst for the electroreduction of Zn²⁺ ions.     

Comparison of mouse plasma and brain tissue homogenate sample pretreatment methods prior to high‐performance liquid chromatography for a new 1,2,4‐triazole derivative with anticonvulsant activity

The focus of the study was to develop a bio‐analytical assay for a 1,2,4‐triazole derivative from plasma and brain tissue homogenate samples. The goal was to compare analytical techniques that facilitate high accuracy with simplified sample processing. In this study, commonly used standard protein precipitation and solid‐phase extraction methods utilizing C₁₈ and cartridges of Hybrid technology were compared in terms of their ability for sample pretreatment and removal of biological matrices before high‐performance liquid chromatography quantification. Fast classical reversed‐phase chromatography on a C₁₈ column paired with selective sample preparation using Hybrid solid‐phase extraction technology resulted in the most precise bio‐analytical determination of the hydrophobic 1,2,4‐triazole derivative in both biological samples studied. The obtained recovery values were above 95% with the coefficient of variation lower than 5%.     

Decompositions of categories over posets and cohomology of categories

Let ? be a small category. We present some results which describe cohomology groups and homotopy colimits of functors defined over ? using cohomology groups and homotopy colimits over certain categories associated to functors from ? to posets. Received: 3 May 1999     

Komplexchemie P‐reicher Phosphane und Silylphosphane. XXV. Bildung und Struktur des [{cyclo‐P3(PtBu2)3}{Ni(CO)2}{Ni(CO)3}]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXV. Formation and Structure of [{ cyclo ‐P₃(P^tBu₂)₃}{Ni(CO)₂}{Ni(CO)₃}] ^tBu₂P–P=P(R)^tBu₂ (R = Br, Me) reacts with [Ni(CO)₄] yielding [{cyclo‐P₃(P^tBu₂)₃}{Ni(CO)₂}{Ni(CO)₃}]. The two cis‐^tBu₂P substituents of the cyclotriphosphane, which results from the trimerization of the phosphinophosphinidene ^tBu₂P–P, are coordinating to a Ni(CO)₂ unit forming a five‐membered P₄Ni chelate ring. The trans‐^tBu₂P group is linked to a Ni(CO)₃ unit. The compound crystallizes in the orthorhombic space group Pbca (No. 61) with a = 933.30(5), b = 2353.2(1) and c = 3474.7(3) pm.     

Reaktionen von tBu2P–P=P(Me)tBu2 mit (Et3P)2NiCl2 und [{η2‐C2H4}Ni(PEt3)2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXIII. Reactions of ^tBu₂P–P=P(Me)^tBu₂ with (Et₃P)₂NiCl₂ and [{η²‐C₂H₄}Ni(PEt₃)₂] ^tBu₂P–P=P(Me)^tBu₂ ( 1 ) forms with (Et₃P)₂NiCl₂ ( 2 ) and Na(Nph) the [μ‐(1,3 : 2,3‐η‐^tBu₂P₄^tBu₂){Ni(PEt₃)Cl}₂] ( 3 ) as main product. Using Na/Hg instead as reducing agent the Ni⁰ compounds [{η²‐^tBu₂P–P}Ni(PEt₃)₂] ( 4 ), [{η²‐^tBu₂P–P=P–P^tBu₂}Ni(PEt₃)₂] ( 5 ) and [(Et₃P)Ni(μ‐P^tBu₂)]₂ ( 6 ) with four‐membered Ni₂P₂ ring result. [{η²‐C₂H₄}Ni(PEt₃)₂] yields with 1 also 4 . The compounds were characterized by ¹H and ³¹P{¹H} NMR investigations and 3 also by a single crystal X‐ray analysis. It crystallizes triclinic in the space group P 1 with a = 1129.4(2), b = 1256.8(3), c = 1569.5(3) pm, α = 72.44(3)°, β = 70.52(3)° and γ = 74.20(3)°.     

Polish Varieties of Industrial Hemp and Their Utilisation in the Efficient Production of Lignocellulosic Ethanol

Nowadays, more and more attention is paid to the development and the intensification of the use of renewable energy sources. Hemp might be an alternative plant for bioenergy production. In this paper, four varieties of Polish industrial hemp (Białobrzeskie, Tygra, Henola, and Rajan) were investigated in order to determine which of them are the most advantageous raw materials for the effective production of bioethanol. At the beginning, physical and chemical pretreatment of hemp biomass was carried out. It was found that the most effective is the alkaline treatment with 2% NaOH, and the biomasses of the two varieties were selected for next stages of research: Tygra and Rajan. Hemp biomass before and after pretreatment was analyzed by FTIR and SEM, which confirmed the effectiveness of the pretreatment. Next, an enzymatic hydrolysis process was carried out on the previously selected parameters using the response surface methodology. Subsequently, the two approaches were analyzed: separated hydrolysis and fermentation (SHF) and a simultaneous saccharification and fermentation (SSF) process. For Tygra biomass in the SHF process, the ethanol concentration was 10.5 g∙L⁻¹ (3.04 m³·ha⁻¹), and for Rajan biomass at the SSF process, the ethanol concentration was 7.5 g∙L⁻¹ (2.23 m³·ha⁻¹). In conclusion, the biomass of Polish varieties of hemp, i.e., Tygra and Rajan, was found to be an interesting and promising raw material for bioethanol production.     

Bioactive Properties of a Novel Antibacterial Dye Obtained from Laccase-Mediated Oxidation of 8-Anilino-1-naphthalenesulfonic Acid

Fungal laccase obtained from a Cerrena unicolor strain was used as an effective biocatalyst for the transformation of 8-anilino-1-naphthalenesulfonic acid into a green-coloured antibacterial compound, which can be considered as both an antimicrobial agent and a textile dye, simultaneously. The process of biosynthesis was performed in buffered solutions containing methanol as a co-solvent, allowing better solubilisation of substrate. The transformation process was optimised in terms of the buffer pH value, laccase activity, and concentrations of the substrate and co-solvent. The crude product obtained exhibited low cytotoxicity, antibacterial properties against Staphylococcus aureus and Staphylococcus epidermidis, and antioxidant properties. Moreover, the synthesised green-coloured compound proved non-allergenic and demonstrated a high efficiency of dyeing wool fibres.     

Growth morphology of crystals from kinetic and geometric perspective

The growth morphology of crystals is analysed from macroscopic point of view and the recent developments in this field are surveyed. In particular, it is shown that, for specific geometry characterized by interfacial angles a given face can increase in size for a very wide range of relative growth rates and need not be the slow‐growing face. Even growing faster than the neighbouring faces, such a face can increase in its size. However, there are other faces with other specific geometry, which can decrease the size growing more slowly than one of the neighbouring faces. If the growth time is sufficiently long, such a face may disappear and not be represented in the final crystal morphology. In the present survey the concepts given earlier [5] are extended. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)