1,3‐Bis[2‐(dimethylaminomethyl)phenyl]triselenide

The title compound, C₁₈H₂₄N₂Se₃, consists of discrete molecules; owing to the presence of strong intramolecular N...Se interactions [N...Se = 2.671 (4) and 2.873 (4) Å], the chalcogen Se atoms of the angular Se₃ chain exhibit different coordination geometries, i.e. the terminal Se atoms are tricoordinated and exhibit a T‐shaped environment of the CNSe₂ core [N...Se—Se = 173.73 (9) and 172.29 (9)°], while the central Se atom is dicoordinated to the other two Se atoms, with an Se—Se—Se angle of 108.32 (2)°.     

Lipase active-site-directed anchoring of organometallics: metallopincer/protein hybrids

The work described herein presents a strategy for the regioselective introduction of organometallic complexes into the active site of the lipase cutinase. Nitrophenol phosphonate esters, well known for their lipase inhibitory activity, are used as anchor functionalities and were found to be ideal tools to develop a single-site-directed immobilization method. A small series of phosphonate esters, covalently attached to ECE "pincer"-type d8-metal complexes through a propyl tether (ECE=[C6H3(CH2E)(2)-2,6]-; E=NR2 or SR), were designed and synthesized. Cutinase was treated with these organometallic phosphonate esters and the new metal-complex/protein hybrids were identified as containing exactly one organometallic unit per protein. The organometallic proteins were purified by membrane dialysis and analyzed by ESI-mass spectrometry. The major advantages of this strategy are: 1) one transition metal can be introduced regioselectively and, hence, the metal environment can potentially be fine-tuned; 2) purification procedures are facile due to the use of pre-synthesized metal complexes; and, most importantly, 3) the covalent attachment of robust organometallic pincer complexes to an enzyme is achieved, which will prevent metal leaching from these hybrids. The approach presented herein can be regarded as a tool in the development of regio- and enantioselective catalyst as well as analytical probes for studying enzyme properties (e.g., structure) and, hence, is a "proof-of-principle design" study in enzyme chemistry.     

Thermal behavior of different cocoa powder varieties and their physicochemical,phytochemical and microbiological characteristics

Four cocoa powder varieties processed in different European countries (Germany, Poland, Romania and Bulgaria) were subjected to physicochemical, phytochemical and microbiological analysis. The cocoa powders were extensively characterized by recording their pH and titratable acidity, respectively, the polyphenols and also the methylxantine derivatives content (theobromine and caffeine). The cocoa powders pH ranged between 5.37 and 8.23, while the titratable acidity was 3.2–4.3 miliequivalent (100 g)^?1 of cocoa powder. Their total polyphenols content ranged between 0.986?÷?2.003 g GAE/(100 g)^?1. The methylxanthine derivatives (theobromine and caffeine) were analyzed by the HPLC method and ranges of 0.992–1.174% for theobromine and 0.096–0.369% for caffeine were obtained. Thermal analysis (TG–DTA) combined with mass spectrometry (MS) elucidated the decomposition processes and the volatile substances (CO, CO₂, H₂O, NO, theobromine, caffeine). The thermal analysis revealed transformations in the cocoa powders composition: drying and water loss; decomposition of pectic polysaccharides; lipids, amino acids and proteins, crystalline phase transformations and carbonizations. The microbiological analysis tested the degree of preservation of the cocoa powders across time, specifically immediately after unwrapping and after 14 days.

     

Thermal decomposition kinetics of some aromatic azomonoethers

Thermal analysis of three azomonoether dyes, exhibiting liquid-crystalline properties, was performed in dynamic air atmosphere. Thermal stability studies and the evaluation of the kinetic parameters of each physical or chemical transformations are essential for a full characterization, before attempting accurate thin films’ depositions of such materials used in non-linear optical applications. New synthesized dyes with general formula: where R is a nematogenic group: CN, CF₃ or a highly polarizable group: NO₂ were investigated using TG, DTG, DTA and DSC techniques, under non-isothermal regime. The evolved gases were analyzed by FTIR spectroscopy. The activation energies of the first decomposition step were evaluated for each compound, the obtained results revealing complex mechanisms.     

Synthesis, characterisation and thermal behaviour of some thiosulfato-and sulfato copper(II) complexes

The investigation concerning the synthesis, spectrochemical and biological properties as well as thermal stability of some tiosulfato-and sulfato copper(II) complexes of type [Cuphen(S₂O₃)(H₂O)_n]·mH₂O (phen: 1,10-phenanthroline; (1): n=2, m=0; (2): n=2, m=0.5) and respectively [Cuphen(OSO₃)(H₂O)_n] ((3): n=0; (4): n=2) are presented in this paper. The bonding and stereochemistry of the complexes have been characterised by IR and electronic studies. The in vitro qualitative and quantitative assays of the antimicrobial activity of the tested compounds vs. planktonic and adherent Gram negative bacterial strains isolated from different surfaces in the hospital environment demonstrated that all compounds exhibited very good antimicrobial activity vs. Escherichia coli, Klebsiella sp. and Enterobacter sp. with very low M.I.C. values. The thermal analysis has evidenced the thermal intervals of stability and also the thermodynamics effects that accompany them both in synthetic air and argon. The thermal behaviour is complex according to DTG and DSC curves including dehydration as well as thiosulfate and phenanthroline decomposition.     

Molecules with new topologies derived from hydrogen-bonded dimers of tetraurea calix[4]arenes

Tetraurea calix[4]arenes 2 have been synthesized in which two adjacent aryl urea residues are connected to a loop by an aliphatic chain -O-(CH(2))(n)-O-. The remaining urea residues have a bulky 3,5-di-tert-butylphenyl residue and an omega-alkenyloxyphenyl residue. Since this bulky residue cannot pass through the loop, only one homodimer (22) is formed in apolar solvents, for steric reasons, in which the two alkenyl residues penetrate the two macrocyclic loops. Covalent connection of these alkenyl groups by olefin metathesis followed by hydrogenation creates compounds 3, which consist of molecules with hitherto unknown topology. Their molecular structure was confirmed by (1)H NMR spectroscopy and ESIMS, and for one example by single-crystal X-ray analysis.     

Investigation of the properties of fully reacted unstoichiometric polydimethylsiloxane networks and their extracted network fractions

We investigated the linear dynamic response of a series of fully reacted unstoichiometric polydimethylsiloxane networks and of the two corresponding network fractions namely the sol and the washed network. The sol and the washed network were separated by a simple extraction process. This way, it was possible to obtain rheological data from the washed network without interference from the sol fraction and furthermore from the sol fraction without interference from the elastic washed network. When the stoichiometry increased towards perfectly reacted networks and beyond, we observed harder networks both qualitatively and by rheology, and the properties of the two fractions became more and more different. At the gel point, the sol fraction and the washed networks have more or less identical properties which our data also show. The storage and loss moduli, G′ and G″, were analysed with the gel equation as proposed by Winter and Chambon (J Rheol 30:367–382, 1986) and Chambon and Winther (J Rheol 31:683–697, 1987). We observed that one of the investigated samples which before the swelling experiment did not show any elastic response gave an elastic washed network after swelling; this was verified by analysis with the gel equation. We also calculated the weight fraction of the sol fraction by using the theory by Villar et al. (Macromolecules 29(11):4072–4080, 1996) and compared this with experimentally found values.     

Preformulation studies for atorvastatin calcium

This paper deals with the study of compatibility between antihyperlipidemic agent atorvastatin calcium trihydrate (ATV) and eight pharmaceutical excipients used in the development of solid dosage forms, namely citric acid, anhydrous lactose, magnesium citrate, magnesium carbonate, sodium carboxymethyl cellulose, polyvinylpyrrolidone K30, colloidal silica and sorbitol. As investigational tools, universal attenuated total reflectance Fourier transform infrared spectroscopy and powder X-ray diffractogram patterns were used for binary mixtures of ATV with each excipient at ambient condition and then completed by subjecting the samples to thermal stress using thermal analysis (TG/DTG/HF), in non-isothermal conditions and in oxidative medium. It was shown the binary mixtures do not present interactions between ATV and excipients when stored under ambient conditions for 2 months, while under thermal stress, ATV presents interactions with sorbitol.

     

Gauge covariance of the Aharonov–Bohm phase in noncommutative quantum mechanics

The gauge covariance of the wave function phase factor in noncommutative quantum mechanics (NCQM) is discussed. We show that the naive path integral formulation and an approach where one shifts the coordinates of NCQM in the presence of a background vector potential leads to the gauge non-covariance of the phase factor. Due to this fact, the Aharonov–Bohm phase in NCQM which is evaluated through the path-integral or by shifting the coordinates is neither gauge invariant nor gauge covariant. We show that the gauge covariant Aharonov–Bohm effect should be described by using the noncommutative Wilson lines, what is consistent with the noncommutative Schrödinger equation. This approach can ultimately be used for deriving an analogue of the Dirac quantization condition for the magnetic monopole.     

Comparison of Different Extraction Solvents for Characterization of Antioxidant Potential and Polyphenolic Composition in Boletus edulis and Cantharellus cibarius Mushrooms from Romania

Edible mushrooms are well-known for their nutritional benefits and low energy density. In addition, mushroom extracts contain various bioactive compounds that account for their antioxidant activity; the applied extraction conditions influence the extraction efficiency of such compounds. Therefore, this study investigates the effects of four extractants on the content of polyphenols and antioxidant properties of Boletus edulis and Cantharellus cibarius mushrooms, aiming to optimize the extraction process. Powders of B. edulis and C. cibarius mushrooms were subjected to extraction with acidic water (10% CH₃COOH), ethanol/water/acetic acid (15:76.5:8.5, v/v/v), hexane, and diethyl ether to measure their total phenolic content (TPC), total flavonoid content (TFC), and Trolox equivalent antioxidant capacity (TEAC). Furthermore, the level of individual polyphenolic compounds in these extracts was quantified using an HPLC-DAD-ESI-MS method. Results showed that the type of solvent significantly influenced the TPC and TEAC of mushroom powder but insignificantly influenced the TFC. A very strong positive correlation was found between TPC and TEAC, but no correlation was found between TFC and TEAC or TPC and TFC. Acidic water extracted the highest amount of polyphenolic compounds from these mushroom powders. Therefore, the aqueous extract showed the highest TPC and strongest antioxidant activity. Thus, acidic water is recommended for polyphenol analysis in B. edulis and C. cibarius mushrooms.