Radicals produced by gamma-irradiation of hyperquenched glassy water containing 2'-deoxyguanosine-5'-monophosphate

Hyperquenched glassy water (HGW) has been suggested as the best model for liquid water, to be used in low-temperature studies of indirect radiation effects on dissolved biomolecules (Bednarek et al. J. Am. Chem. Soc. 1996, 118, 9387). In the present work, these effects are examined by X-band electron spin resonance spectroscopy (ESR) in gamma-irradiated HGW matrix containing 2'-deoxyguanosine-5'-monophosphate. Analysis of the complex ESR spectra indicates that, in addition to OH(*) and HO2(*) radicals generated by water radiolysis, three species are trapped at 77 K:(i) G(C8)H(*) radical, the H-adduct to the double bond at C8; (ii) G(- *) radical anion, the product of electron scavenging by the aromatic ring of the base; and (iii) dR(-H)(*) radicals formed by H abstraction from the sugar moiety, predominantly at the C'5 position. We discuss the yields of the radicals, their thermal stability and transformations, as well as the effect of photobleaching. This study confirms our earlier suggestion that in HGW the H atom addition/abstraction products are created at 77 K in competition with HO2(*) radicals, in a concerted process following ionization of water molecule at L-type defect sites of the H-bonded matrix. The lack of OH(*) reactivity toward the solute suggests that the H-bonded structure in HGW is much more effective in recombining OH(*) radicals than that of aqueous glasses obtained from highly concentrated electrolyte solutions. Furthermore, complementary experiments for the neat matrix have provided evidence that HO2(*) radicals are not the product of H atom reaction with molecular oxygen, possibly generated by ultrasounds used in the process of sample preparation.     

On a general bilinear functional equation

Aequationes mathematicae - Let X, Y be linear spaces over a field $${\mathbb {K}}$$ . Assume that $$f :X^2\rightarrow Y$$ satisfies the general linear equation with respect to the first...     

Combinatorial synthesis and characterization of metal-open frameworks in mild and friendly conditions: application to CO₂ adsorption

Combinatorial screening using precipitation methods at room temperature can lead to a great diversity of carboxylate based Metal Organic Frameworks (MOFs) including already known or original porous solids. The investigation of the synthesis of MOFs in different solvent and solvent mixtures includes the use of solvents such as alcohols and tetrahydrofuran (THF) which would greatly facilitate large scale production. We also show the application of Principal Component Analysis (PCA) and clustering techniques on large libraries of XRD diffraction files in order to identify classes of similar phases and peculiar phases. The combinatorial screening of 105 samples in the La/btc system has led to the identification of two phases which are solvent depending. On the La(btc) compound, the CO? adsorption measurements reveal a guest-host interactions as supported by XRD phase transformation upon thermal treatment. The mass transport can be assigned to a "single file diffusion" regime due to the one dimensional channel porous structure associated to small pore size.     

Performance of different separation methods interfaced in the same MS-reflection TOF detector: a comparison of performance between CE versus HPLC for biomarker analysis

One of the aims in the field of proteomics is the identification of a protein or polypeptide, or a range of these compounds, that could provide pre-symptomatic indication of the onset of a disease. A number of analytical techniques have been employed to try and achieve this end. These techniques have been applied to the complete range of body fluids and tissues that are readily available from clinical studies. Of these sample sources, the urinary low molecular weight peptidome has been shown to reflect changes in the health status of the individual. The alterations that occur in the polypeptide make up of urine, which reflect changes in biological status, are known as biomarkers. To be able to determine these changes no single technique has emerged that can cope with detecting the large number of peptides present and quantifying them over the wide concentration range they exist in. In this investigation, we made use of a single reflectron time of flight (RTOF)-MS analyser to which we first connected a CE system and then a nanoflow HPLC. Two pooled male and female standard urine samples were compared on these systems. Both techniques had similar results in terms of number of peptides detected and the mass range the peptides were detected over. The major differences in terms of biomarker research were the ability in CE to calibrate the migration time of the peptides to allow comparison between samples. In addition, CE was shown not to suffer from carry over from previous samples as was seen in the LC analysis.     

Thermodynamics of oxygen in dilute liquid silver–tellurium alloys

Abstract  

The activity coefficient of oxygen in liquid Ag and binary Ag–Te dilute alloys were determined between 1,285 and 1,485 K by coulometric titration using the electrochemical cell (Ir, [O] in liquid metal or alloy | yttria stabilized zirconia | air, Pt). The experimental and evaluation procedures described in the literature were adopted. The oxygen activity coefficient was determined in pure liquid silver to be . Next, the oxygen activity coefficient in dilute Ag–(Te)–O alloys for variable X _Te content (from 0.01 to 0.06) was measured. From the obtained results, Wagner’s interaction parameter as a function of temperature was derived in the form . The electrochemical coulometric titration method seems to be very useful to study the thermodynamics of oxygen interaction in liquid silver and its alloys.     

Generic Extensions of Prinjective Modules

Let be an algebraically closed field and let be a finite partially ordered set of finite prinjective type. We study generic extensions of prinjective modules over the incidence -algebra of . We prove that there exist generic extensions of prinjective -modules and describe properties of the monoid of generic extensions.Partially supported by Polish KBN Grant 5 P0 3A 015 21.     

Identification of catecholamines in the immune system by desorption/ionization on silicon

Desorption/ionization from porous silicon dioxide (DIOSD), in combination with a standard matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) instrument, was used for the identification of catecholamines in the human peripheral blood lymphocytes. A routine MALDI-TOF analysis does not allow for sensitive detection of low molecular mass compounds (i.e. below 400 Da) due to the pronounced background ions arising from the matrix. Therefore, we have tested DIOSD methodology for the identification of catecholamines in the immune system. Using DIOSD, catecholamines were unambiguously identified in the cell extract of peripheral blood lymphocytes at the femtomolar level. The DIOSD extends the possible use of MALDI-TOF mass spectrometry towards small molecules that were previously detected by other methods.     

The influence of the cyclopeptide sequence on its coordination abilities towards Cu(II)

The binding abilities of three novel cyclohexapeptides with three histidyl residues are presented. The analysis of the potentiometric and spectroscopic results, together with the theoretical calculations, allow the characterization of the coordination abilities of c(GlyHisArgHisHisGly), c(GlyHisArgHisGlyHis), c(GlyHisArgGlyHisHis) towards copper(II) ions and the impact of the peptide sequence on the efficiency in Cu(II) binding, and the type of formed complexes is also presented.     

Invariance of quasi-arithmetic means with function weights

Let I⊂R be a non-trivial interval and let . We present some results concerning the following functional equation, generalizing the Matkowski-Sutô equation,

λ(x,y)φ⁻¹(μ(x,y)φ(x)+(1−μ(x,y))φ(y))+(1−λ(x,y))ψ⁻¹(ν(x,y)ψ(x)+(1−ν(x,y))ψ(y))=λ(x,y)x+(1−λ(x,y))y,     

Synthesis,Pharmacological Evaluation,and Computational Studies of Cyclic Opioid Peptidomimetics Containing β3-Lysine

Our formerly described pentapeptide opioid analog Tyr-c[D-Lys-Phe-Phe-Asp]NH₂ (designated RP-170), showing high affinity for the mu (MOR) and kappa (KOR) opioid receptors, was much more stable than endomorphine-2 (EM-2) in the rat brain homogenate and displayed remarkable antinociceptive activity after central (intracerebroventricular) and peripheral (intravenous ) administration. In this report, we describe the further modification of this analog, which includes the incorporation of a β³-amino acid, (R)- and (S)-β³-Lys, instead of D-Lys in position 2. The influence of such replacement on the biological properties of the obtained analogs, Tyr-c[(R)-β³-Lys-Phe-Phe-Asp]NH₂ (RP-171) and Tyr-c[(S)-β³-Lys-Phe-Phe-Asp]NH₂, (RP-172), was investigated in vitro. Receptor radiolabeled displacement and functional calcium mobilization assays were performed to measure binding affinity and receptor activation of the new analogs. The obtained data revealed that only one of the diastereoisomeric peptides, RP-171, was able to selectively bind and activate MOR. Molecular modeling (docking and molecular dynamics (MD) simulations) suggests that both compounds should be accommodated in the MOR binding site. However, in the case of the inactive isomer RP-172, fewer hydrogen bonds, as well as instability of the canonical ionic interaction to Asp¹⁴⁷, could explain its very low MOR affinity.