Hybrid sol–gel thin films doped with a pH indicator: effect of organic modification on optical pH response and film surface hydrophilicity

Optical sensors for application in innovative wearable sensing systems such as textile-integrated systems and wireless sensor platforms rely on the development of low-cost multifunctional materials compatible with standard fabrication technologies. We are developing optically responsive pH sensitive sol–gel coatings for integration with a mobile wireless smart tag sensing system. For this application, we have fabricated a range of thin pH sensitive films using bromocresol green (BCG) indicator immobilised in inorganic–organic silica hybrid matrices prepared by a sol–gel method and deposited by spin-coating onto glass substrates. The surface hydrophilicity of the films were varied by using the inorganic sol–gel precursor tetraethoxysilane together with either methyltriethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane or glycidoxypropyltrimethoxysilane as organically modified sol–gel precursors, co-polymerised in different ratios. Spectral characterisation of the films was performed using visible absorption spectroscopy. The shift in absorption maxima and other spectral changes of the different matrices have been identified, and the apparent pK _app values of the immobilised BCG pH indicator determined. The surface wettability properties of the films have been studied by measuring the contact angle of water, formamide and diiodomethane which has allowed the estimation of the surface free energy (SFE) using three different models: Owens–Wendt, Wu and van Oss-Chaudhury-Good. It is shown that the SFE of the hybrid films is directly related to the type and the degree of organic modification, which in turn has a significant effect on the pH response-time of these sensing films.     

Concentration of 137Cs and 40K in meat of omnivore and herbivore game species in mountain forest ecosystems of Gorski Kotar, Croatia

The aim of this study was to investigate ¹³⁷Cs and ⁴⁰K load in large mammal game species in the mountain forest region of Gorski Kotar in Croatia approximately a quarter of century after the Chernobyl accident. ¹³⁷Cs and ⁴⁰K activity were determined by the gamma-spectrometric method in 49 meat samples of five large game species: brown bear (Ursus arctos), wild boar (Sus scrofa), roe deer (Capreolus capreolus), red deer (Cervus elaphus), and chamois (Rupicapra rupicapra). The results indicated that herbivore game species (roe deer, red deer and chamois) show significantly lower ¹³⁷Cs concentrations than omnivore species (brown bear, wild boar), thereby confirming the hypothesis that different dietary strategy impact caesium concentrations in meat. The measured caesium load in brown bear meat was in the range of two orders of magnitude, while caesium load in wild boar meat was found in the range of one order of magnitude. The estimated effective equivalent dose showed that uptake of the highest caesium doses would be from consumption of omnivore species meat, while much lower doses could be taken in with the consumption of meat from herbivore species.     

Guanidiniocarbonyl-pyrrole-aryl conjugates as nucleic acid sensors: switch of binding mode and spectroscopic responses by introducing additional binding sites into the linker

Two novel guanidiniocarbonyl pyrrole-pyrene conjugates 3 and 4 as spectroscopic probes for ds-polynucleotides were synthesized and their interaction with different ds-DNAs/RNAs studied. Compared to a previously reported first set of conjugates (1 and 2) the significant extension and increased rigidity of the central part of the structure resulted in a switch of DNA binding mode from intercalative (previously studied derivatives 1 and 2 with a nonbinding and flexible linker) to minor groove binding of the two novel guanidiniocarbonyl-pyrrole-pyrene conjugates 3 and 4. These two compounds interact strongly with ds-DNAs, but only weakly with ds-RNA. The newly incorporated heterocyclic moieties within the central part of the structure of 3 and 4 were able to control by steric and hydrogen-bonding effects the alignment of the molecules within various, structurally different forms of DNA minor grooves, whereby even small differences in the position of the attached pyrene within the groove were reflected in different fluorimetric responses. In addition, 3 and 4 revealed intriguing in vitro selectivity among various human tumour cell lines.     

Government Formation Problem

Central European Journal of Operations Research - In addition to the same political and ideological attitudes, members of political parties can be interconnected at private and/or professional...     

Maximum information entropy principle and the interpretation of probabilities in statistical mechanics − a short review

In this paper an alternative approach to statistical mechanics based on the maximuminformation entropy principle (MaxEnt) is examined, specifically its close relation withthe Gibbs method of ensembles. It is shown that the MaxEnt formalism is the logicalextension of the Gibbs formalism of equilibrium statistical mechanics that is entirelyindependent of the frequentist interpretation of probabilities only as factual (i.e.experimentally verifiable) properties of the real world. Furthermore, we show that,consistently with the law of large numbers, the relative frequencies of the ensemble ofsystems prepared under identical conditions (i.e. identical constraints) actuallycorrespond to the MaxEnt probabilites in the limit of a large number of systems in theensemble. This result implies that the probabilities in statistical mechanics can beinterpreted, independently of the frequency interpretation, on the basis of the maximuminformation entropy principle.     

Guanidiniocarbonylpyrrole–Aryl Derivatives: Structure Tuning for Spectrophotometric Recognition of Specific DNA and RNA Sequences and for Antiproliferative Activity

We present a systematic study of different guanidiniocarbonylpyrrole‐aryl derivatives designed to interact with DNA or RNA both through intercalation of an aromatic moiety into the base stack of the nucleotide and through groove binding of a guanidiniocarbonylpyrrole cation. We varied 1) the size of the aromatic ring (benzene, naphthalene, pyrene and acridine), 2) the length and flexibility of the linker connecting the two binding groups, and 3) the total number of positive charges present at different pH values. The compounds and their interactions with DNA and RNA were studied by UV/Vis, fluorescence and CD spectroscopy. Antiproliferative activities against human tumour cell lines were also determined. Our studies show that efficient interaction with, for example, DNA requires a significantly large aromatic ring (pyrene) connected through a flexible linker to the pyrrole moiety. However, a positive charge, as in 12 , is also needed. Compound 12 allows for base‐pair‐selective recognition of ds‐DNA at physiological pH values. The antiproliferative activities of these compounds correlate with their binding affinities towards DNA, suggesting that their biological effects are most probably due to DNA binding.     

Macroscopic Time Evolution and MaxEnt Inference for Closed Systems with Hamiltonian Dynamics

MaxEnt inference algorithm and information theory are relevant for the time evolution of macroscopic systems considered as problem of incomplete information. Two different MaxEnt approaches are introduced in this work, both applied to prediction of time evolution for closed Hamiltonian systems. The first one is based on Liouville equation for the conditional probability distribution, introduced as a strict microscopic constraint on time evolution in phase space. The conditional probability distribution is defined for the set of microstates associated with the set of phase space paths determined by solutions of Hamilton’s equations. The MaxEnt inference algorithm with Shannon’s concept of the conditional information entropy is then applied to prediction, consistently with this strict microscopic constraint on time evolution in phase space. The second approach is based on the same concepts, with a difference that Liouville equation for the conditional probability distribution is introduced as a macroscopic constraint given by a phase space average. We consider the incomplete nature of our information about microscopic dynamics in a rational way that is consistent with Jaynes’ formulation of predictive statistical mechanics, and the concept of macroscopic reproducibility for time dependent processes. Maximization of the conditional information entropy subject to this macroscopic constraint leads to a loss of correlation between the initial phase space paths and final microstates. Information entropy is the theoretic upper bound on the conditional information entropy, with the upper bound attained only in case of the complete loss of correlation. In this alternative approach to prediction of macroscopic time evolution, maximization of the conditional information entropy is equivalent to the loss of statistical correlation, and leads to corresponding loss of information. In accordance with the original idea of Jaynes, irreversibility appears as a consequence of gradual loss of information about possible microstates of the system.