The Role of Triazole and Glucose Moieties in Alkali Metal Cation Complexation by Lower-Rim Tertiary-Amide Calix[4]arene Derivatives

The binding of alkali metal cations with two tertiary-amide lower-rim calix[4]arenes was studied in methanol, N,N-dimethylformamide, and acetonitrile in order to explore the role of triazole and glucose functionalities in the coordination reactions. The standard thermodynamic complexation parameters were determined microcalorimetrically and spectrophotometrically. On the basis of receptor dissolution enthalpies and the literature data, the enthalpies for transfer of reactants and products between the solvents were calculated. The solvent inclusion within a calixarene hydrophobic basket was explored by means of ¹H NMR spectroscopy. Classical molecular dynamics of the calixarene ligands and their complexes were carried out as well. The affinity of receptors for cations in methanol and N,N-dimethylformamide was quite similar, irrespective of whether they contained glucose subunits or not. This indicated that sugar moieties did not participate or influence the cation binding. All studied reactions were enthalpically controlled. The peak affinity of receptors for sodium cation was noticed in all complexation media. The complex stabilities were the highest in acetonitrile, followed by methanol and N,N-dimethylformamide. The solubilities of receptors were greatly affected by the presence of sugar subunits. The medium effect on the affinities of calixarene derivatives towards cations was thoroughly discussed regarding the structural properties and solvation abilities of the investigated solvents.     

Polyphenols and Antioxidant Activity of Citrus Fiber/Blackberry Juice Complexes

The objective of this study was to investigate the use of citrus fiber as a carrier of blackberry juice polyphenols. For that purpose, freeze-dried complexes with blackberry juice and different amounts of citrus fiber (1%, 2% and 4%) were prepared. Complexes were evaluated spectrophotometrically for total polyphenols, proanthocyanidins and antioxidant activity. Analyses of individual polyphenols were performed using high-performance liquid chromatography. IR spectra were recorded to confirm encapsulation. All analyses were performed after preparation and after eight months of storage, in order to examine the stability of formed complexes. The obtained results indicated that increasing the amount of fiber led to a decrease in the concentration of polyphenols and the antioxidant activity of complexes. Cyanidin 3-glucoside was the prevalent anthocyanin in complexes (138.32–246.45 mg/100 g), while cyanidin 3-dioxalylglucoside was present at lower concentrations (22.19–31.45 mg/100 g). The other identified and quantified polyphenols were hesperidin (from citrus fiber), ellagic acid and quercetin (1317.59–1571.65 mg/100 g, 31.94–50.11 mg/100 g and 20.11–33.77 mg/100 g, respectively). Degradation of polyphenols occurred during storage. Results obtained in this study confirmed that citrus fiber could be used for the formulation of novel bioactive additives. Such additives could enhance the antioxidant potential of products to which they are added, such as baked goods, dairy, or fruit products.     

Multidimensional Jensen’s operator on a Hilbert space and applications

Motivated by a joint concavity of connections, solidarities and multidimensional weighted geometric mean, in this paper we extend an idea of convexity (concavity) to operator functions of several variables. With the help of established definitions, we introduce the so called multidimensional Jensen’s operator and study its properties. In such a way we get the lower and upper bounds for the above mentioned operator, expressed in terms of non-weighted operator of the same type. As an application, we obtain both refinements and converses for operator variants of some well-known classical inequalities. In order to obtain the refinement of Jensen’s integral inequality, we also consider an integral analogue of Jensen’s operator for functions of one variable.     

Further bounds for hardy type differences

In this paper we define a functional as a difference between the right-hand side and left-hand side of the refined Boas type inequality using the notation of superquadratic and subquadratic functions and study its properties, such as exponential and logarithmic convexity. We also, state and prove improvements and reverses of new weighted Boas type inequalities. As a special case of our result we obtain improvements and reverses of the Hardy inequality and its dual inequality. We introduce new Cauchy type mean and prove monotonicity property of this mean.     

Bounds for Hardy type differences

Let A _k be an integral operator defined by

Thermodynamics of Complexation of Alkali Metal Cations by a Lower-Rim Calix[4]arene Amino Acid Derivative

Complexation of alkali metal cations with 5,11,17,23-tetra-tert-butyl-26,28,25,27-tetrakis(O-methyl-d-α-phenylglycylcarbonylmethoxy)calix[4]arene (L) in methanol and acetonitrile was studied by means of direct and competitive microcalorimetric titrations at 25 °C. The thermodynamic parameters of complexation reactions showed that all the reactions investigated were enthalpically controlled. In both solvents the reaction enthalpy was most favorable for Na⁺ binding with L leading to the highest affinity of the examined calix[4]arene derivative towards this cation. The solubilities (and consequently the solution Gibbs energies) of the ligand were determined, as were the corresponding solution enthalpies and entropies. No significant difference was observed between the solution thermodynamic quantities of L in the two solvents, whereas the transfer of complex species from methanol to acetonitrile was found to be quite favorable. The interactions of solvent molecules with the free and the complexed ligand were investigated by ¹H NMR spectroscopy. It was concluded that in both cases inclusion of an acetonitrile molecule into the hydrophobic cavity of L occurred, which significantly affected the cation complexation in this solvent. The thermodynamic data were discussed regarding the structural properties of the ligand, the free and the complexed cations as well as the solvation abilities of the solvents examined. In this respect, the specific solvent-solute interactions and the intramolecular NH⋅⋅⋅O=C hydrogen bonds at the lower rim of L were particularly addressed.     

Highly Ordered Mesoporous Cobalt Oxide Nanostructures: Synthesis,Characterisation, Magnetic Properties,and Applications for Electrochemical Energy Devices

Highly ordered mesoporous Co₃O₄ nanostructures were prepared using KIT‐6 and SBA‐15 silica as hard templates. The structures were confirmed by small angle X‐ray diffraction, high resolution transmission electron microscopy, and N₂ adsorption–desorption isotherm analysis. Both KIT‐6 cubic and SBA‐15 hexagonal mesoporous Co₃O₄ samples exhibited a low Néel temperature and bulk antiferromagnetic coupling due to geometric confinement of antiferromagnetic order within the nanoparticles. Mesoporous Co₃O₄ electrode materials have demonstrated the high lithium storage capacity of more than 1200 mAh g^?1 with an excellent cycle life. They also exhibited a high specific capacitance of 370 F g^?1 as electrodes in supercapacitors.     

Proteomic biomarker discovery: it's more than just mass spectrometry

The previous decade witnessed an enormous number of studies with the singular goal of identifying protein biomarkers for diseases such as cancer. A large majority of these studies have focused on comparative studies of serum or plasma obtained from disease-affected and control patients. In these studies, proteins identified in the samples using MS were compared with the hope that differences between samples would reveal useful biomarkers. Unfortunately, finding clinically relevant biomarkers has often been elusive and frustrating. As with most research efforts, both successes and failures, much has been learned about what strategies work and which do not. Part of the problem can be attributed to underestimating the effort required to discover novel biomarkers and depending too heavily on MS analysis of peripheral blood samples. Fortunately, the future for biomarker discovery still appears bright. MS technology continues to increase in sensitivity, throughput, and accuracy while novel types of samples and clever experimental designs coupled with innovative bioinformatics will make this vision of routine biomarker discovery a reality. To achieve ultimate success is going to require concomitant application of a number of different technologies, all providing the information necessary for discovering and validating clinically useful biomarkers.     

A New Linear Shell Model for Shells with Little Regularity

In this paper, a new model of linearly elastic shell is formulated. The model is of Koiter’s type capturing the membrane and bending effects. However, the model is well formulated for shells with little regularity, namely the shells whose middle surface is parameterized by a W ^1,∞ function. Unknowns in the model are the displacement \(\tilde{\boldsymbol {u}}\) of the middle surface of the shell and the infinitesimal rotation \(\tilde{\boldsymbol {\omega}}\) of the shell cross-section. The existence and uniqueness of the solution of the model has been proved for \((\tilde{\boldsymbol {u}}, \tilde{\boldsymbol {\omega}}) \in H^{1} \times H^{1}\) with the help of the Lax-Milgram lemma. The model is analyzed asymptotically with respect to the small thickness of the shell. It is shown that the model asymptotically behaves just as the membrane model, the flexural model, and the generalized membrane model in each regime. In this way the model is justified. Since the model is well formulated for shells whose middle surface is with corners, we compare the model with Le Dret’s model of folded plates. It turns out that in the regime of the flexural shells the models are the same. The differential equations of the model are derived. They imply that the model is as a special case of the Cosserat shell model with a single director for a particular constitutive law.     

Analyticity on circles for rational and real-analytic functions of two real variables

Conditions for rational and real-analytic functions of two real variables to be holomorphic are given in terms of holomorphic extendibility from families of circles. The first author was supported by the Israel Science Foundation, grant No. 279/02-1. The second author was partially supported by a grant from the Slovenian Ministry of Science and Technology. Both authors were supported by the Ministry of Science of Israel and the Ministry of Science and Technology of Slovenia, in the framework of the Program of Exchange by scientists.